EP2018362A1 - Verfahren zur herstellung von alpha-hydroxycarbonsäureestern - Google Patents

Verfahren zur herstellung von alpha-hydroxycarbonsäureestern

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Publication number
EP2018362A1
EP2018362A1 EP07727424A EP07727424A EP2018362A1 EP 2018362 A1 EP2018362 A1 EP 2018362A1 EP 07727424 A EP07727424 A EP 07727424A EP 07727424 A EP07727424 A EP 07727424A EP 2018362 A1 EP2018362 A1 EP 2018362A1
Authority
EP
European Patent Office
Prior art keywords
pressure
bar
alpha
ammonia
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Withdrawn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
EP07727424A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alexander May
Bernd Vogel
Hermann Siegert
Jochen Ackermann
Sönke BRÖCKER
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
Priority claimed from DE200610022896 external-priority patent/DE102006022896A1/de
Priority claimed from DE102007011706A external-priority patent/DE102007011706A1/de
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2018362A1 publication Critical patent/EP2018362A1/de
Withdrawn legal-status Critical Current

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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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • 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
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to processes for the production of alpha-hydroxycarboxylic acid esters on an industrial scale.
  • the invention relates to a continuous process for the preparation of alpha-hydroxycarboxylic acid esters according to the preamble of claim 1.
  • alkyl (meth) acrylates Alpha-hydroxycarboxylic acid esters are valuable intermediates in the large-scale synthesis of acrylic acid esters and methacrylic acid esters, hereinafter referred to as alkyl (meth) acrylates.
  • alkyl (meth) acrylates find their main application in the preparation of polymers and copolymers with other polymerizable compounds.
  • methacrylic acid esters such as, for example, methyl methacrylate
  • HIBSM Hydroxyisobutyrate
  • a generic method is known from EP 0 945 423. "Disclosed herein is a process for producing alpha-hydroxycarboxylic acid esters, which comprises the steps of reacting an alpha-hydroxycarboxylic acid amide and an alcohol in the presence of a catalyst in a liquid phase while maintaining the ammonia concentration in the reaction solution at 0, 1 wt .-% or less holds that emerging ammonia is removed as gas in a gas phase.
  • reaction solution As a gas in the gas phase, it is distilled off from the reaction solution.
  • the reaction solution is heated to boiling and / or a strip gas, i. an inert gas bubbled through the reaction solution.
  • Another object of the invention was to provide a process in which the alpha-hydroxycarboxylic acid esters can be obtained very selectively.
  • the present invention accordingly relates to continuous processes for the preparation of alpha-hydroxycarboxylic acid esters in which alpha-hydroxycarboxylic acid amide is reacted with an alcohol in the presence of a catalyst to give reacting a product mixture comprising alpha-hydroxycarboxylic acid esters, ammonia, unreacted alpha-hydroxycarboxylic acid amide, and alcohol and catalyst; wherein the method is characterized in that one
  • Eduktstöme comprising as starting materials an alpha-hydroxycarboxylic acid, an alcohol and a catalyst fed into a pressure reactor; the educt streams in the pressure reactor at a pressure in the range of 1 bar to 100 bar with each other; and the product mixture depleted of alcohol and ammonia, wherein ammonia in a
  • Strip agents are distilled off.
  • the ammonia resulting from the reaction according to the invention can be separated off relatively easily from the alcohol, for example methanol, which is used for the alcoholysis or methanolysis of the alpha-hydroxycarboxylic acid amide. This is possible, although alcohol or methanol and ammonia are very difficult to separate in dissolved form under normal conditions.
  • the alcohol for example methanol, which is used for the alcoholysis or methanolysis of the alpha-hydroxycarboxylic acid amide.
  • ammonia already accumulates in a very pure form and can thus be reused in various processes without further purification step.
  • the alcohol also accumulates in such a way that it is present in process-suitable quality and can be recycled, for example, into a production process.
  • the process of the invention avoids the use of aids for the separation of the ammonia, above all the use of inert gases as a stripping agent for the ammonia becomes unnecessary. Accordingly, in the process according to the invention, no larger amount of additional inert gas flow, which in turn would have to be separated from the ammonia, is produced. •
  • the process according to the invention gives the alpha-hydroxycarboxylic acid esters in high yields and purities. This applies in particular in comparison with the processes described in EP-A-0945423, in which the ⁇ -hydroxycarboxamides are subjected to alcoholysis to give the alpha-hydroxycarboxylic acid esters while maintaining a very low actual ammonia concentration in the liquid phase.
  • the process of the present invention also has an extremely low tendency to form by-products.
  • the method according to the invention can be carried out inexpensively, in particular with low energy consumption.
  • the catalysts used for the alcoholysis of the alpha-hydroxycarboxamide can be used over a long period of time, without the selectivity or the activity decreases. In this respect, the catalysts have a long service life.
  • alpha-hydroxycarboxylic acid esters are prepared by the reaction between the reactants alpha-hydroxycarboxamide and alcohol in the presence of a catalyst.
  • the alpha-hydroxycarboxamides which can be used in the reaction of the invention usually include all those carboxamides which have at least one hydroxyl group in the alpha position relative to the carboxylic acid amide group.
  • Carboxylic acid amides are well known in the art. Commonly included herein are compounds having groups of the formula - CONR'R "-, wherein R 'and R" independently represent hydrogen or a 1-30 carbon group comprising in particular 1-20, preferably 1-10 and especially 1-5 carbon atoms ,
  • the carboxylic acid amide may comprise 1, 2, 3, 4 or more groups of the formula - CONR'R "- These include, in particular, compounds of the formula R (-CONR'R") n , where R is a 1-30 carbon atom group which in particular comprises 1-20, preferably 1-10, in particular 1-5 and particularly preferably 2-3, carbon atoms, R 'and R "have the abovementioned meaning and n is an integer in the range of 1-10, preferably 1 4 and more preferably 1 or 2 represents.
  • the term "1 to 30 carbon atoms” denotes residues of organic compounds having 1 to 30 carbon atoms.
  • aromatic and heteroaromatic groups it 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 are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O.
  • Aromatic or heteroaromatic groups which are preferred 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,
  • the 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, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
  • the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
  • Preferred heteroaliphatic groups include the aforementioned preferred alkyl and cycloalkyl groups in which at least one carbon moiety is replaced by O, S or a group NR 8 or NR 8 R 9 and R 8 and R 9 are independently 1 to 6 carbon atoms having alkyl, having 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, in particular 1 to 4 carbon atoms and cycloalkyl or cycloalkyloxy groups having 3 to 20 carbon atoms, preferably 5 to 6 carbon atoms.
  • the radical R may have substituents.
  • substituents are i.a. Halogens, in particular fluorine, chlorine, bromine, and alkoxy or hydroxy radicals.
  • alpha-hydroxycarboxamides can be used in the process of the invention individually or as a mixture of two or three or more different alpha-hydroxycarboxamides.
  • Particularly preferred alpha-hydroxycarboxylic acid amides include alpha-hydroxyisobutyric acid amide and / or alpha-hydroxyisopropionic acid amide.
  • alpha-hydroxycarboxamides which are obtainable by cyanohydrin synthesis from ketones or aldehydes and hydrogen cyanide.
  • the carbonyl compound for example a ketone, in particular acetone, or an aldehyde, for example acetaldehyde, propanal, butanal, is reacted here with hydrocyanic acid to give 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 cyanohydrin thus obtained is reacted with water to the alpha-hydroxycarboxylic acid amide.
  • 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-A-0945429, EP-A-0561614 and EP-A-0545697.
  • This can be the Manganese oxide can be used in the form of manganese dioxide, which by treatment of manganese sulfate with potassium permanganate under acidic conditions (see Biochem.J., 50 p 43 (1951) and J. Chem.Soc, 1953, p 2189, 1953) or by electrolytic oxidation of manganese sulfate in aqueous solution is obtained.
  • the catalyst is often used in the form of powder or granules with a suitable grain size.
  • the catalyst can be applied to a support.
  • so-called slurry reactors or fixed-bed reactors can also be used here, which can also be operated as a trickle bed and are described inter alia in EP-A-956 898.
  • the hydrolysis reaction can be catalyzed by enzymes. Suitable enzymes include nitrile hydratases. This reaction is exemplary in "Screening, Characterization and Application of Cyanide-resistant Nitrile Hydratases" Eng. Life. Be. 2004, 4, no. 6 described.
  • the hydrolysis reaction can be catalyzed by acids, especially sulfuric acid. This is stated inter alia in JP Hei 4-193845.
  • Alcohols which can be used successfully 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 alpha-hydroxycarboxamides in the sense of alcoholysis.
  • the reaction of the ⁇ -hydroxycarboxylic acid amide is preferably carried out by alcoholysis with an alcohol which preferably comprises 1-10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • Preferred alcohols are i.a.
  • 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.
  • alkyl formates can be used.
  • methyl formate or a mixture of methanol and carbon monoxide are suitable.
  • the reaction between alpha-hydroxycarboxamide and alcohol is carried out in the context of the invention in a pressure reactor.
  • This is basically a reaction space to understand, which allows it during the implementation of an overpressure maintain.
  • Overpressure in this context means a pressure greater than atmospheric pressure, ie 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. It follows from the above that the pressure during the reaction / alcoholysis of the alpha-hydroxycarboxamide according to the invention as well as during the removal / removal of the ammonia from the product mixture is greater than atmospheric pressure or greater than 1 bar. In particular, this means that the ammonia formed during the reaction is distilled off from the mixture under a pressure of greater than 1 bar, wherein the use of auxiliaries such as strip gas for distillative removal of the ammonia is completely dispensed with.
  • the product mixture is depleted not only in ammonia but also in unreacted alcohol.
  • 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.
  • this includes continuous processes for the preparation of alpha-hydroxycarboxylic acid esters in which alpha-hydroxycarboxamide is reacted with an alcohol in the presence of a catalyst to give a product mixture containing the alpha-hydroxycarboxylic acid esters, ammonia, unreacted alpha-hydroxycarboxamide and alcohol and Catalyst comprises; the process being characterized in that a) reactant streams comprising as starting materials an alpha-hydroxycarboxylic acid amide, an alcohol and a catalyst are fed into a pressure reactor; b) reacting the educt streams in the pressure reactor at a pressure in the range of greater than 1 bar to 100 bar with each other; c) discharging the product mixture resulting from step b) comprising alpha-hydroxycarboxylic acid ester, unreacted alpha-hydroxycarboxylic acid amide and catalyst from the pressure reactor; and d) depleting the product mixture of alcohol and ammonia, wherein ammonia is distilled off at a pressure which is kept
  • a particularly expedient process modification provides that b1) the educts in the pressure reactor are reacted together at a pressure in the range from 5 bar to 70 bar; b2) the product mixture resulting from step b1) is expanded to a pressure less than the pressure in the pressure reactor and greater than 1 bar; d) feeding the resulting from step b2) relaxed product mixture in a distillation column; c2) distilling off ammonia and alcohol overhead in the distillation column, the pressure in the distillation column being kept in the range from greater than 1 bar to less than or equal to 10 bar; and d1) the ammonia-alcohol-depleted product mixture resulting from step c2) comprising alpha-hydroxycarboxylic acid ester, unconverted alpha-hydroxycarboxylic acid amide and catalyst is discharged from the column.
  • reaction of the educts and separation of ammonia / alcohol take place in two different spatially separated aggregates.
  • reactor / reaction space and separation unit for the separation of ammonia / alcohol from the product mixture are separated from each other.
  • the quality features mentioned can be further improved by repeating the reaction in the pressure reactor once or several times with the product mixture depleted in ammonia and alcohol in the bottom of the separation column (pressure distillation column), the reaction step being shifted to a plurality of pressure reactors connected in series are.
  • a process variant which is characterized in that e) the product mixture discharged in step d1) is compressed to a pressure in the range from 5 to 70 bar is particularly preferred. f) the thus compressed according to step e) compressed mixture for reaction in another pressure reactor and react again; and g) repeating steps b2), d), c2) and d1) according to the aforementioned list.
  • This process step can be repeated as desired, for example, three to four repetitions are particularly favorable.
  • preference is given to a process which is characterized in that the reaction in the pressure reactor, the expansion of the reacted mixture, the feed to the first distillation column, the depletion of ammonia and alcohol in the first distillation column, the removal of the depleted mixture, compression and Feed of the depleted mixture into a further pressure reactor is repeated several times, wherein a n-fold depleted in ammonia and alcohol product mixture is obtained at the bottom of the pressure distillation column depending on the number n of series-connected pressure reactors.
  • n can be a positive integer greater than zero.
  • n is in the range of 2 to 10.
  • An expedient method modification provides that the above-mentioned and defined steps e) to g) are repeated several times.
  • Very specific process variants comprise carrying out the reaction and depletion four times using four series-connected pressure reactors to give a product mixture which has been depleted in ammonia and alcohol four times. Accordingly, this process variant is characterized in that steps e) to g) are repeated at least twice, so that the reaction is carried out in total in at least four pressure reactors connected in series.
  • the Product mixture preferably only partially depleted in alcohol.
  • the alcohol can also be supplied separately to the respective reaction.
  • the reaction according to step c) can be carried out at a higher pressure than the distillation of the ammonia according to step d).
  • the pressure difference is at least 10 bar, more preferably at least 40 bar and most preferably at least 50 bar.
  • the pressure distillation column generally and preferably at a temperature in the range of about 50 0 C to about 160 0 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 ° C - 240 0 C. It is particularly useful to lower the temperature from reactor to reactor, for example in steps in the range of 3 - 15 ° C, preferably 4 - 10 0th C and especially useful in 5 ° C increments. As a result, the selectivity of the reaction is positively influenced.
  • Another measure to increase the selectivity may also be to reduce the reactor volume from reactor to reactor. With decreasing reactor volume with increasing conversion one likewise obtains an improved selectivity.
  • the reduction in reactor volume may be in the range of 1% to 50%, more preferably 2% to 20%, and most preferably 5% to 10%, based on the volume of the larger reactor.
  • the various measures for increasing the selectivity can be combined here with particular advantage.
  • the skilled person can easily optimize the selectivity by the variation of pressure, temperature and residence time.
  • the reaction for example, at a temperature in the range be carried out from 200 to 220 0 C, wherein the residence time can be optimized.
  • the reaction can be repeated several times, it being possible hereby to achieve a particularly expedient reaction procedure, ie high selectivity at low cost.
  • the distance of the removal point to the bottom (column bottom) of the column is used for orientation as a relative location.
  • This process variant may advantageously be distinguished by the fact that the reaction according to step b) is carried out at a pressure in the range from 20 bar to 90 bar, more preferably from 40 bar to 80 bar and most preferably from 50 bar to 70 bar.
  • the distillation of the ammonia according to step d) may preferably be carried out at a pressure in the range of 1, 2 bar to 10 bar, more preferably 1, 5 bar to 3 bar.
  • reaction step and the removal step in a single unit.
  • Pressure reactor and pressure distillation column are realized in a single unit, fall together, so to speak.
  • this includes continuous processes for the preparation of alpha-hydroxycarboxylic acid esters in which the starting materials are alpha-hydroxycarboxamide with an alcohol in the presence of a Reacting the catalyst to obtain a product mixture comprising alpha-hydroxycarboxylic acid esters, ammonia, unreacted alpha-hydroxycarboxylic acid amide, and alcohol and catalyst; the process being characterized in that a ') starting material streams comprising, as starting materials, an alpha-hydroxycarboxylic acid amide, an alcohol and a catalyst are fed into a pressure reactor; b ') the educt streams in the pressure reactor at a pressure in the range of 1 bar to 100 bar with each other; c ') depleting the product mixture of alcohol and ammonia, wherein ammonia is distilled off at a pressure which is constantly greater than 1 bar, without the aid of additional striping agents; and d ') discharging from step c') resulting ammonia and alcohol depleted product mixture comprising a ') starting material
  • a preferred embodiment of the invention comprises carrying out steps a ') to c') simultaneously in a reactive distillation column at a pressure in the range of 2 bar to 50 bar, preferably 5 bar to 40 bar.
  • Particularly useful is a method which is characterized in that one carries out the steps a ') to c') simultaneously in a reactive distillation column at a pressure in the range of 10 bar to 30 bar.
  • the reaction of the educts is carried out in a reactive distillation column designed as a pressure column and the resulting ammonia is continuously distilled off during the reaction over the top of the column.
  • a reactive distillation column designed as a pressure column and the resulting ammonia is continuously distilled off during the reaction over the top of the column.
  • the reaction temperature of the reactions according to the invention can vary over a wide range, with the reaction rate generally increasing with increasing temperature.
  • the upper temperature limit generally results from the boiling point of the alcohol used.
  • the reaction temperature is in the range of 40-300 0 C, more preferably 120-240 0 C and most preferably 180 ° C to 220 ° C.
  • the reaction system may be advantageous if at most 10 wt .-%, preferably at most 5 wt .-% and particularly preferably at most 1 wt .-% of the alcohol in the reaction phase are removed from the reaction system via the gas phase.
  • the reaction can be carried out particularly inexpensively.
  • the reaction system is advantageous in that it is constantly kept under a pressure of greater than 1 bar.
  • the reaction system may comprise in particular the regions of the system in which the reaction takes place and the regions of the system in which the ammonia is separated from the products and the alcohol, in particular the distillation columns.
  • the separation of ammonia and alcohol can preferably be carried out at a pressure greater than 1 bar, particularly preferably greater than 1.5 bar, with a very high efficiency.
  • the residence time may be 30 seconds to 2 hours, more preferably 1 minute to 30 minutes, and most preferably 2 minutes to 15 minutes. These data are preferably based on the reactor volume. In the case of several reactors, the sum of the volumes of the pressure reactors is used in this case, without the volume of the distillation apparatus being included. In the Use of reactive still gives rise to the residence times corresponding to the volume of the reactive still.
  • any multi-stage pressure-resistant distillation column can be used, which preferably has two or more separation stages.
  • the number of separation stages in the present invention refers to the number of plates in a tray column or the number of theoretical plates in the case of a packed column or a packed column.
  • Examples of a multistage distillation column with trays include those such as bubble trays, sieve trays, tunnel trays, valve trays, slotted trays, sieve slotted trays, sieve trays, nozzle trays, centrifugal trays, for a multistage distillation column with packing such as Raschig rings, Lessing rings, Pall Rings, Berl saddles, Intalox saddles and for a multistage distillation column with packings such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz) and catalyst bag packs, for example Kata-Pak.
  • packing such as Raschig rings, Lessing rings, Pall Rings, Berl saddles, Intalox saddles
  • packings such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz) and catalyst bag packs, for example Kata-Pak.
  • a distillation column having combinations of regions of soils, regions of packing or regions of packing may also be used.
  • the ammonia-depleted product mixture has inter alia the desired alpha-hydroxycarboxylic acid ester.
  • the ammonia-depleted product mixture can be removed via the bottom of the distillation column and fed to another second distillation column, where to obtain a depleted of both ammonia and alcohol mixture the alcohol over the top of the column in a convenient process modification distilled off and preferably recycled to a reactor.
  • a process is preferred in which the mixture depleted in ammonia and alcohol is discharged via the bottom of the further distillation column and still another distillation column feeds, in which one distils off the alpha-hydroxycarboxylic acid ester overhead and the thus obtained at ammonia, alcohol and alpha-hydroxycarboxylic acid depleted mixture, optionally after further purification steps, recycled to the reactor.
  • the alpha-hydroxycarboxylic acid ester product obtained from the top of the column is of high purity and can, for example, be supplied in an extremely advantageous manner to further reaction steps for obtaining alkyl (meth) acrylates.
  • the distillation apparatus preferably has at least one region, called a reactor, in which at least one catalyst is provided.
  • This reactor may, as described, preferably be within the distillation column.
  • the described procedure can tolerate a broad spectrum of proportions of the educts.
  • the reaction according to the invention takes place in the presence of a catalyst.
  • the reaction can be accelerated, for example, by basic catalysts. These include homogeneous catalysts as well as heterogeneous catalysts.
  • lanthanoid compounds as catalysts, water-resistant lanthanoid compounds being particularly preferred.
  • the use of this type of homogeneous catalysts in a process of the invention is novel and leads to surprisingly advantageous results.
  • water resistant means that the catalyst retains its catalytic ability in the presence of water. Accordingly, the reaction according to the invention can be carried out in the presence of up to 2% by weight of water, without the catalytic ability of the catalyst thereby being significantly impaired.
  • essential means that the reaction rate and / or the selectivity decreases by at most 50%, based on the reaction without the presence of water.
  • Lanthanoid compounds denote compounds of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Td, Dy, Ho, Er, Tm, Yb, and / or Lu.
  • a lanthanoid compound is used which comprises lanthanum.
  • the lanthanide compound has a solubility in water of at least 1 g / l, preferably at least 10 g / l at 25 ° C.
  • Preferred lanthanoid compounds are salts which are preferably present in the oxidation state 3.
  • Particularly preferred water-resistant lanthanoid compounds are La (N0s) 3 and / or LaCU. These compounds can be added as salts of the reaction mixture or formed in situ.
  • a particular process variant involves using as the catalyst a soluble metal complex containing titanium and / or tin and the alpha-hydroxycarboxamide.
  • the catalyst used is a metal trifluoromethanesulfonate.
  • the metal is selected from the group consisting of the elements in groups 1, 2, 3, 4, 11, 12, 13 and 14 of the Periodic Table.
  • preference is given to using those metal trifluoromethanesulfonates in which the metal corresponds to one or more lanthanides.
  • heterogeneous catalysts include, inter alia, magnesium oxide, calcium oxide and basic ion exchangers and the like.
  • the catalyst is an insoluble metal oxide which comprises at least one selected from among Sb, Sc, V, La, Ce, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Fe, Co, Ni, Cu, Al, Si, Sn, Pb and Bi group selected element.
  • the catalyst used is an insoluble metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Cu, Ga, In, Bi and Te.
  • ammonia released in the alcoholysis in the process of the invention can then be easily recycled, for example, to an overall process for the preparation of alkyl (meth) acrylates.
  • ammonia can be converted to hydrocyanic acid with methanol. This is set forth, for example, in EP-A-0941984.
  • the hydrocyanic acid can be obtained from ammonia and methane according to the BMA or Andrussow process, these processes being described in Ullmann's Encyclopedia of Industrial Chemistry 5th edition on CD-ROM, keyword "Inorganic Cyano Compounds.”
  • the ammonia in an ammoxidation process such as, for example, the large-scale synthesis of acrylonitrile from ammonia, oxygen and propene.
  • the acrylonitrile synthesis is described under the heading Sohio process in Indutrial Organic Chemistry by K. Weisermehl and H. -J. Arpe on page 307 ff , General process sequence of a first variant according to the invention with reference to FIG. 1
  • the alcoholysis preferably methanolysis
  • the alcoholysis can take place in the combination of a pressure rectification column and a plurality of pressure reactors shown in FIG.
  • the Hydroxyisocarbonklareamid for example, Hydroxyisobutyramid
  • methanol via line (2)
  • methanol / catalyst mixture via line (3)
  • a first pressure reactor R-1
  • a reaction mixture of the hydroxyisocarboxylic acid ester and ammonia, unreacted hydroxyisocaboxylic acid amide and methanol, catalyst and traces of a by-product are formed in the reactor (R-1).
  • this mixture After leaving the reactor (R-1), this mixture is expanded to a lower pressure and passed via line (5) into a pressure column (K-1).
  • the column is preferably equipped with packings. There, the ammonia is separated from the reaction mixture with a portion of the methanol and recovered at the top as a distillate.
  • the higher-boiling components, the hydroxyisocarboxylic acid ester, the by-product and the unreacted hydroxyisobutyramide are withdrawn from the column with the remaining methanol, compressed to reactor pressure and fed to the second pressure reactor (R-2).
  • the reaction is preferably carried out in 4 pressure reactors connected in series (R-1 to R-4).
  • the product mixture leaving the column (K-1) via the bottom consists of the hydroxyisocarboxylic acid ester, traces of a by-product and the hydroxyisobutyramide. It is passed through line (9) into the still (K-2). There, the hydroxyisocarboxylic ester precipitates as distillate and is withdrawn via line (10).
  • the Hydroxyisocarbonklareamid / catalyst mixture leaves the column (K-2) via the bottom and is partially passed via the lines (12) and (4) back into the first pressure reactor (R-1). A partial flow (11) is fed to a thin-film evaporator (D-1). This allows the discharge of a mixture of amide, the high-boiling by-product and the catalyst via line (13).
  • the alcoholysis preferably methanolysis done in the plant set forth in Figure 2.
  • the Hydroxyisocarbon Acidmid for example Hyrodroxyisobutyramid, via line (1) together with methanol via line (2) and a methanol / catalyst mixture via line (3) a
  • Reactive distillation column (K-1) supplied.
  • the column is designed as a pressure column and preferably equipped with trays.
  • a reaction mixture of hydroxyisocarboxylic acid ester and ammonia, unreacted hydroxyisocaboxylic acid amide and methanol, catalyst and traces of a by-product forms on the plates of the column.
  • the ammonia is obtained as distillate and is withdrawn via line (7).
  • the high-boiling components, the hydroxyisocarboxylic acid ester, the by-product and the unreacted educts hydroxyisobutyramide and methanol leave the column through the bottom. Via line (6), this mixture is passed into another distillation (K-2).
  • Table 1 shows further examples, which were carried out in the specified experimental apparatus at a molar feed ratio of MeOH: HI BA of 14: 1, but different reaction temperatures and residence times.
  • a methanol / catalyst mixture with a catalyst content of 1.0% by weight and alpha-hydroxyisobutyramide in a molar ratio of 7: 1 were continuously metered in over an experimental period of 48 h.
  • the reaction to HIBSM and ammonia was carried out at a pressure of 75 bar and a reaction temperature of 220 0 C with a residence time of 5 min.
  • the reaction was carried out using La (NOs) 3 as a catalyst.
  • the resulting product mixture was analyzed by gas chromatography. The molar selectivity to alpha relative to hydroxyisobutyramide
  • a methanol / catalyst mixture with a catalyst fraction of 0.9% by weight and alpha-hydroxyisobutyramide in a molar ratio of 10: 1 were continuously metered in over an experimental period of 48 h.
  • the reaction to HIBSM and ammonia was carried out at a pressure of 75 bar and a reaction temperature of 200 and 220 0 C with a residence time of 5 min or 10 min.
  • the reaction was carried out using La (NOs) 3 as a catalyst.
  • the resulting product mixture was analyzed by gas chromatography. The molar selectivity to alpha relative to hydroxyisobutyramide

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP07727424A 2006-05-15 2007-03-28 Verfahren zur herstellung von alpha-hydroxycarbonsäureestern Withdrawn EP2018362A1 (de)

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DE200610022896 DE102006022896A1 (de) 2006-05-15 2006-05-15 Verfahren zur Herstellung von Alpha-Hydroxycarbonsäuren
US89378807P 2007-03-08 2007-03-08
DE102007011706A DE102007011706A1 (de) 2007-03-08 2007-03-08 Verfahren zur Herstellung von Alpha-Hydroxycarbonsäuren
PCT/EP2007/052951 WO2007131829A1 (de) 2006-05-15 2007-03-28 Verfahren zur herstellung von alpha-hydroxycarbonsäureestern

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DE102014205304A1 (de) 2014-03-21 2015-09-24 Evonik Industries Ag Verfahren zur Abtrennung von Ammoniak aus alkoholischer Lösung in Gegenwart von Kohlensäureverbindungen
DE102016210285A1 (de) 2016-06-10 2017-12-14 Evonik Röhm Gmbh Verfahren zur Herstellung von Methacrylaten und Methacrylsäure
US10227284B2 (en) 2014-09-10 2019-03-12 Evonik Roehm Gmbh Method for preparing alpha-hydroxycarboxylic acid esters in which ammonia is recycled

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DE102016210285A1 (de) 2016-06-10 2017-12-14 Evonik Röhm Gmbh Verfahren zur Herstellung von Methacrylaten und Methacrylsäure

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CA2652315A1 (en) 2007-11-22
US8569539B2 (en) 2013-10-29
JP2009537471A (ja) 2009-10-29
WO2007131829A1 (de) 2007-11-22
KR101365790B1 (ko) 2014-02-20
JP5517610B2 (ja) 2014-06-11
MX2008014641A (es) 2008-11-27

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