EP2870131A1 - Procédé pour produire de la vanilline à partir de compositions aqueuses basiques contenant de la vanilline - Google Patents

Procédé pour produire de la vanilline à partir de compositions aqueuses basiques contenant de la vanilline

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Publication number
EP2870131A1
EP2870131A1 EP13734066.7A EP13734066A EP2870131A1 EP 2870131 A1 EP2870131 A1 EP 2870131A1 EP 13734066 A EP13734066 A EP 13734066A EP 2870131 A1 EP2870131 A1 EP 2870131A1
Authority
EP
European Patent Office
Prior art keywords
vanillin
aqueous
basic
lignin
adsorbent
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Withdrawn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
EP13734066.7A
Other languages
German (de)
English (en)
Inventor
Florian Stecker
Andreas Fischer
Axel Kirste
Agnes Voitl
Chung Huan Wong
Siegfried Waldvogel
Carolin REGENBRECHT
Dominik SCHMITT
Marius Franziskus HARTMER
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13734066.7A priority Critical patent/EP2870131A1/fr
Publication of EP2870131A1 publication Critical patent/EP2870131A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • B01D15/363—Anion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/014—Ion-exchange processes in general; Apparatus therefor in which the adsorbent properties of the ion-exchanger are involved, e.g. recovery of proteins or other high-molecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/07—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing anionic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the present invention relates to a process for the recovery of vanillin from aqueous, basic vanillin-containing compositions, as obtained, for example, in the oxidation of alkaline, aqueous lignin-containing solutions or suspensions.
  • Lignin as well as lignin-containing substances such as alkali lignin, lignin sulfate or lignin sulfonate, fall as waste or by-products of wood processing into pulp.
  • the total production of lignin-containing substances is estimated at around 20 billion tonnes per year.
  • alkali lignin which can be prepared by alkaline treatment of the black liquor obtained in papermaking, is used in North America as a binder for wood and cellulose-based press plates, as a dispersant, for clarifying sugar solutions, stabilizing asphalt emulsions.
  • waste lignin is produced by combustion as an energy source, e.g. used for the pulp process.
  • the biopolymer lignin is a group of three-dimensional macromolecules found in the cell wall of plants, composed of various phenolic monomer units such as p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. Due to its composition, it represents the only significant aromatic source of nature. Moreover, the use of this renewable natural product does not compete with its use as food.
  • Vanillin 4-hydroxy-3-methoxybenzaldehyde
  • Vanillin is a synthetic flavoring agent widely used as a flavoring agent for foods, as a fragrance in deodorants and perfumes, as well as flavor enhancers of pharmaceuticals and vitamin supplements instead of expensive natural vanilla.
  • Vanillin is also an intermediate in the synthesis of various drugs, e.g. L-dopa, methyldopa and papaverine.
  • vanillin or vanillate from basic lignin solutions succeeds, for example, via cation exchange, with neutralization of the basic solution.
  • the vanillate is passed over a cation exchange resin in the H + form, whereby it is protonated to vanillin.
  • This cation exchange is coupled with a neutralization in the presence of a buffer solution (vanillate / vanillin) - see M. Zabkova et al., Sep. Purif. Technol. 2007, 55, 56-68.
  • a disadvantage is that the vanillin is not extracted from the solution. Thus, this method offers no protection against overoxidation.
  • large amounts of acid are needed to neutralize the basic reaction medium. Acidification causes the lignin to precipitate out of solution, requiring filtration to cause a loss of vanillin due to filtration.
  • CH 245671 describes the recovery of vanillin from aqueous solutions containing impurities, wherein the aqueous solution is first the vanillin adsorbed on a basic ion exchanger, which has amino groups, and then eluted with an acid. In the examples, this is from the aqueous Solutions the humic acid contained precipitated by acidification and then the aqueous solution of vanillin adjusted to pH 7.
  • Precipitation of the lignin can be avoided by e.g. Sodium vanillate is extracted directly from the alkaline solution with n-butyl alcohol or isopropanol.
  • this extraction is limited by the lack of solubility of the vanillate salts in organic solvents.
  • this method has a negative effect that the extracted portion of unreacted lignin is very large and thus removed from the oxidation.
  • the process should be particularly suitable for obtaining vanillin from alkaline, aqueous compositions, such as those obtained in the oxidation of aqueous alkaline lignin-containing compositions, which, in addition to vanillin, also contain lignin and polymeric oxidation products.
  • These solutions typically have pH values of at least pH 10, often at least pH 12 and especially pH values above pH 13.
  • the process should allow recovery of the vanillin from these compositions without removing larger amounts of lignin along with the vanillin.
  • the process should also be capable of removing vanillin from the aqueous alkaline reaction mixtures resulting from the oxidation during the oxidation process so as to reduce the risk of over-oxidation of the vanillin.
  • an aqueous, basic vanillin-containing composition in particular in particular a composition as obtained in the oxidation, especially in the oxidation by means of electrolysis, of aqueous alkaline lignin-containing compositions, treated with a basic, solid adsorbent, in particular an anion exchanger.
  • the present invention thus relates to a process for obtaining vanillin from an aqueous, basic vanillin-containing composition, in particular from a composition as obtained in the oxidation, especially in the oxidation by means of electrolysis, of aqueous alkaline lignin-containing compositions comprising at least a treatment of an aqueous, basic vanillin-containing composition, in particular the treatment of a composition as obtained in the oxidation, especially in the oxidation by electrolysis, of aqueous alkaline lignin-containing compositions, with a basic, solid adsorbent, in particular an anion exchanger.
  • the process according to the invention has a number of advantages: since the vanillin is present as a weak acid in the alkaline, aqueous composition predominantly or completely in anionic form, i. H. is present as vanillate, it is adsorbed by the adsorbent and can then in a simple manner by treatment with a suitable eluent, typically with an acid, in particular with a dilute solution of a mineral acid in an organic solvent or in an aqueous-organic solvent mixture, released bwz , be eluted. As a result, an acid entry into the basic or alkaline composition can be avoided.
  • the process has the advantage that it can be directly mixed with basic or alkaline solutions of vanillin, which may still contain large amounts of impurities.
  • NEN even at pH values of at least pH 10, in particular at least pH 12 or even at pH values above pH 13 can be performed. It is surprising that vanillin from basic solutions are also adsorbed by the basic adsorbent at these pH values, since, owing to the comparatively low charge density of the vanillate anion and the comparatively high concentration of OH ions at these pH values, Values would have expected that the vanillate anion displace OH - ions and no significant adsorption of the vanillate takes place on the basic adsorbent.
  • the process according to the invention thus enables repeated or continuous oxidation of lignin in the alkaline medium with simultaneous, repeated or continuous recovery of the vanillin.
  • the recovery of vanillin with the aid of the solid basic adsorbent is particularly economical because the basic adsorbent is easily regenerated and can be used repeatedly to recover the vanillin.
  • the basic adsorbent in particular the anion exchange resin
  • the basic adsorbent will be separated from the alkaline aqueous vanillin-containing composition and subsequently the vanillin will be released from the adsorbent by treatment with the eluent.
  • the separation may be carried out by conventional solid-liquid separation methods, e.g. by filtration, sedimentation or centrifugation.
  • the composition will first pass through a bed of the basic adsorbent, for example a column packed with the adsorbent, and then elute the basic adsorbent with the eluent.
  • Suitable adsorbents are basically all substances which have basic groups or are treated with hydroxide ions. These include alkalized activated carbons, basic aluminum oxides, clays, basic adsorber resins, in particular anion exchangers or anion exchanger resins.
  • Anion exchangers or anion exchanger resins generally have functional groups which are selected from tertiary amino groups, quaternary ammonium groups and quaternary phosphonium groups.
  • the anion exchangers used are preferably crosslinked organic polymer resins which have cationic groups, for example quaternary ammonium groups, quaternary phosphonium groups, imidazolium groups or guanidinium groups, in particular quaternary ammonium groups or imidazolium groups.
  • the basic adsorbents used are anion exchange resins from the group of crosslinked polystyrene resins (hereinafter ion exchanger of group i), in which part of the phenyl rings of the crosslinked polystyrene carry quaternary ammonium groups, in particular those of the formula I:
  • R in which R 1 , R 2 and R 3 independently of one another are C 1 -C 5 -alkyl, where one of the radicals R 1 , R 2 or R 3 can also be C 1 -C 8 -hydroxyalkyl, A is C 1 -C 4 -alkanediyl , and # represents the point of attachment to a phenyl group of the polystyrene resin.
  • Ci-Cs-alkyl is a linear or branched aliphatic hydrocarbon radical having 1 to 8 carbon atoms, in particular having 1 to 4 carbon atoms (Ci-C 4 alkyl), such as methyl, ethyl, n- Propyl, isopropyl, n-butyl, 2-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.
  • C 1 -C 8 -hydroxyalkyl is a linear or branched aliphatic hydrocarbon radical having 1 to 8 C atoms, in particular having 2 to 4 C atoms (C 2 -C 4 -hydroxyalkyl), which carries an OH group.
  • examples of such radicals are 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl and
  • C 1 -C 4 -alkanediyl is a bivalent aliphatic hydrocarbon radical having 1 to 4 C atoms, such as methylene (CH), ethane-1, 1-diyl, ethane-1, 2-diyl, propane-2,2 -diyl, propan-1, 2-diyl, propan-1, 3-diyl, butane-1, 1-diyl, butane-2,2-diyl, butane-1, 2-diyl, butane-1, 3-diyl , Butane-2,3-diyl or butane-1, 4-diyl.
  • CH methylene
  • R 1 , R 2 , R 3 independently of one another are methyl or ethyl and especially methyl;
  • Adsorbents of group i) are known and commercially available, for example the Amberlite® types IRA400, IRA401, IRA402, IRA410, IRA458, IRA478, IRA900, IRA904, IRA910, FPA40, FPA90, FPA91 (Dow), Amberlyst® A26 (Dow ), the Amberjet® types 4200, 4400 and 4600 (Dow), the Ambersep® types 900 and 920U (Dow), the Dowex® types Dowex Monosphere 550A OH, Dowex 1 X100, 1 X850 and 1 X850 (DOW) and the Applexion® types XA4001, XA 4013, XA4023, XA4041, XA4042 and XA4043.
  • the basic adsorbents used are anion exchange resins to crosslinked polyvinylpyridines (hereinafter ion exchanger of group ii), in which a part of the pyridine is quaternized, for example as a group of formulas IIa or IIb, in particular for IIa stands:
  • R 4 is Ci-Cs-alkyl, especially Ci-C4-alkyl and especially methyl
  • # represents the point of attachment to a carbon atom of the polymer backbone of the polyvinylpyridine resin.
  • Adsorbents of group ii) are known and commercially available, for example the quaternized Reillex® HP types such as Reillex® HPQ.
  • the basic adsorbents used are anionic exchange resins of crosslinked acrylate resins (in the following, ion exchanger of group iii) in which some of the copolymerized mono- have quaternary ammonium groups, for example as a group of formula III:
  • R 5 , R 6 and R 7 are independently C 1 -C 5 -alkyl, A 'is C 2 -C 4 -alkanediyl, and # is the point of attachment to an oxygen or nitrogen atom of a carboxyl group or carboxamide group attached to the polymer backbone of the acrylate resin.
  • Adsorbents of group iii) are known and commercially available, for example the Applexion® types XA 4122 and XA 4141 (Novasep).
  • Suitable adsorbents are also polymers which have N-C 1 -C 8 -alkylimidazolium groups (hereinafter ion exchangers of group iv).
  • the N-C 1 -C 8 -alkylimidazolium groups are bonded to the polymer backbone directly or via a spacer.
  • Such polymers can be prepared by polymer-analogous reaction with N-C 1 -C 8 -alkylimidazole compounds, for example by reaction of haloalkyl groups, in particular polymers having chlorobenzyl groups, e.g. Copolymers of styrene and chloromethylstyrene with Nd-Cs-alkylimidazoles.
  • imidazolium-containing monomers for example (N-C 1 -C 5 -alkylimidazolium) methylstyrene, N-vinyl-N-C 1 -C 8 -alkylimidazolium, ⁇ - (N-carbonyl) Cs-alkylimidazolium) C 2 -C 8 -alkyl acrylate or ⁇ - (N-C 1 -C 8 -alkylimidazolium) C 2 -C 8 -alkyl methacrylate, optionally with comonomers such as C 1 -C 8 -alkyl acrylates, C 1 -C 8 -alkyl methacrylates, C 2 -C 8 -hydroxyalkyl acrylates , C2-C8 hydroxyalkyl methacrylates or styrene, for example by free radical polymerization or by controlled radical polymer
  • Polymers are known and described, for example, by J. Yuan, M. Antonietti, Polymer 2011, 52, 1469-1482; J. Huang, C. Tao, Q. An, W. Zhang, Y. Wu, X. Li, D. Shen, G. Li, Chemical Communications 2010, 46, 967; R. Marcilla, J. Alberto Blazquez, J. Rodriguez, J.A. Pomposo, D. Mecerreyes, Journal of Polymer Science Part A: Polymer Chemistry 2004, 42, 208-212; J. Tang, H. Tang, W. Sun, M. Radosz, Y. Shen, Journal of Polymer Science Part A: Polymer Chemistry 2005, 43, 5477-5489; J. Tang, Y. Shen, M. Radosz, W. Sun, Industrial & Engineering Chemistry Research
  • the anion exchange resins of groups i), ii), iii) and iv) may be macroporous or gel-like, gel-type anion exchange resins, in particular gel anion exchange resins of group i) being preferably suitable.
  • the charge density, ie the number of ionic groups in anion exchange resins suitable according to the invention, is typically in the range from 0.5 to 5 mmol / g, in particular from 1 to 4.5 mmol / g, of ion exchange resin (dry).
  • the adsorbents or anion exchange resins typically have a capacity for hydroxide (OH) ions in the range from 0.1 to 3 eq / L (molar equivalents per liter, moist), in particular in the range from 0.3 to 2.5 eq / L (wet) and especially in the range of 0.5 to 2 eq / L.
  • OH hydroxide
  • the basic adsorbents are particulate.
  • the mean particle size of the particulate adsorbents is typically in the range from 10 ⁇ m to 2500 ⁇ m, and in particular in the range from 100 ⁇ m to 1000 ⁇ m, and especially in the range from 400 to 1000 ⁇ m.
  • the adsorbents typically have particle sizes in the range of 10 to 650 mesh, especially 15 to 350 mesh, and range in the range of 15 to 60 mesh.
  • the inventively preferred polymer resins may be gel-like or macroporous.
  • the particulate resins are typically in the form of macroscopic polymer particles, for example in the form of a powder or finely divided granules.
  • the mean particle size of the anion exchangers is typically in the range from 10 ⁇ to 2000 ⁇ and in particular in the range of 100 ⁇ to 1000 ⁇ and especially in the range of 400 to 1000 ⁇ (weight average, determined by sieving). They typically have grain sizes in the range of 10 to 650 mesh, especially 15 to 350 mesh, and range in size from 15 to 60 mesh.
  • the adsorbent in particular the anion-exchanger resin
  • the anion-exchanger resin can be used in its OH form, ie. H. for the charge neutralization of the present in the adsorbent, in particular in the anion exchange resin groups are OH ions.
  • the adsorbent, especially the anion exchange resin can also be used in the salt form, i. H. the charge neutralization cationic groups present in the anion exchange resin are non-basic counter ions such as chloride or sulfate.
  • the OH form is then generated by the basic, aqueous vanillin composition and represents the actual adsorbent.
  • the vanillin adsorbed by the adsorbent in the treatment of the aqueous, basic vanillin-containing composition is prepared by treating the adsorbent with less than one adsorbent. At least one eluent desorbs from the adsorbent and can be obtained in this way from the eluent in purified form. Suitable eluents are, above all, solutions of acids, in particular mineral acids in organic solvents, and solutions of acids, in particular mineral acids, in organic-aqueous solvent mixtures.
  • Suitable organic solvents are especially those which are immiscible with water at 22 ° C indefinitely or at least dissolve at 22 ° C in an amount of at least 200 g / L in water. These include above all dimethyl sulfoxide, acetone,
  • C 1 -C 4 -alkanols such as methanol, ethanol, isopropanol, n-propanol, 1-butanol, 2-butanol and tert-butanol, alkanediols, such as glycol, 1,4-butanediol, but also cyclic ethers, such as dioxane, methyltetrahydrofuran or tetrahydrofuran , Nitrogen heterocycles, such as pyridine or N-methylpyrrolidine and mixtures. Preference is given to C 1 -C 4 -alkanols and especially to methanol.
  • the organic solvents can also be used in admixture with water.
  • the proportion of water will preferably not exceed 70% by volume, in particular 50% by volume and especially 30% by volume, based on the total volume of organic solvent and water. If solutions of acids, in particular mineral acids, in organic-aqueous solvent mixtures are used as eluents,
  • solutions of mineral acids such as hydrochloric acid, phosphoric acid, and in particular sulfuric acid are suitable.
  • solutions of organic carboxylic and sulfonic acids in particular those having 1 to 3 carbon atoms, such as methanesulfonic acid, formic acid, acetic acid and propionic acid.
  • the solution of the acid preferably has a concentration of acid in the range from 0.01 to 10 mol kg -1 , in particular from 0.1 to 5 mol kg -1 .
  • the treatment of the aqueous, basic vanillin-containing composition with the adsorbent, in particular the anion exchange resin is generally carried out at temperatures below 150 ° C, often at a temperature below 100 ° C, preferably at a temperature in the range of 10 to 150 ° C. and especially 10 to 100 ° C and especially in the range of 10 to 70 ° C or 15 to 50 ° C.
  • the basic vanillin-containing composition is preferably passed through an adsorbent arrangement, ie by means of an adsorbent arrangement several fixed beds of the adsorbent, for example by one or more columns, with the Adsorbent (eg the anion exchanger) are packed.
  • the transmission can be done both descending and ascending.
  • the passage is preferably carried out at a specific flow rate (specific load) in the range from 0.2 to 35, in particular 0.5 to 10, in particular 1 to 10 bed volumes per hour or a volumetric flow rate in the range of 0.1 to 50 m /H.
  • the relative amount of aqueous alkaline composition and adsorbent is usually selected so that at least 35%, and especially at least 50% of the vanillin contained in the aqueous alkaline composition is adsorbed by the adsorbent.
  • the amount of aqueous, alkaline composition is usually from 1 to 1500 times the amount, in particular from 2 to 1000 times the amount of the bed volume.
  • the adsorbent at the outlet of the adsorber arrangement e.g. the column packed with adsorbent
  • any effluents still contain vanillin, so that the effluent is optionally applied to a further adsorbent arrangement, e.g. a column packed with adsorbent, can be passed.
  • the loading process may be followed by a washing step.
  • water is passed through the adsorbent arrangement.
  • the amount of wash water at this stage is usually 0.1 to 10 times the bed volume, especially 0.5 to 5 times the bed volume.
  • the washing water is generally passed through at a specific flow rate (specific load) in the range from 0.2 to 35, in particular 0.5 to 10, in particular 1 to 10 bed volumes per hour or a volumetric flow rate in the range of 0, 1 to 50 m / h.
  • the resulting wash water may contain small amounts of vanillin and can then be combined with the accumulating during loading effluents.
  • a washing step is not required, so that a preferred embodiment of the process according to the invention does not comprise a washing step and the elution takes place immediately after the loading.
  • the loading or the optionally performed washing step is followed by the elution of the vanillin.
  • the eluent is passed through the Adsorbensanor- tion.
  • the vanillin is desorbed and eluted and the adsorbent, for example, the anion exchange resin, regenerated.
  • the amount of eluent is usually from 0.1 to 20 times the amount, in particular from 0.5 to 10 times the amount, for example, 1 to 8 times the amount of the bed volume.
  • the passage of the eluent is usually carried out with a specific flow rate (specific load) in the range of 0.5 to 20, in particular 1 to 10, in particular 2 to 8 bed volumes per hour.
  • a specific flow rate in the range of 0.5 to 20, in particular 1 to 10, in particular 2 to 8 bed volumes per hour.
  • any cationic groups in the adsorbent are in the salt form.
  • a regeneration in the OH-form be, for example, by treating with an aqueous solution of an alkali metal hydroxide, for example with aqueous NaOH.
  • the elution can be carried out in ascending or descending order.
  • the elution can be carried out in the same direction as the loading or opposite thereto.
  • the elution may be followed by another washing step to remove any impurities present.
  • water is passed through the anion exchanger arrangement.
  • the amount of washing water is usually 0.1 to 10 times, especially 0.5 to 5 times, e.g. 2 to 4 times the bed volume.
  • the washing water is generally passed through at a specific flow rate (specific load) in the range of 0.5 to 20, in particular 1 to 10, in particular 2 to 8 bed volumes per hour.
  • the effluent obtained in the washing step is usually fed as waste water to a conventional wastewater treatment or other workup.
  • the adsorbent assembly may be operated intermittently and then has one or more, e.g. 2, 3 or 4 in-line, stationary packed with adsorbent fixed beds. It can also be operated continuously and then usually has from 5 to 50 and in particular 15 to 40 adsorbent beds, which are e.g. Part of a "True Moving Bed” arrangement (see K. Tekeuchi J. Chem. Eng. Jpn., 1978, 1 1 pp.
  • the eluate obtained in the elution is worked up in a conventional manner to obtain the vanillin, usually the acid is first removed, for example If necessary, the eluate can be concentrated beforehand, for example by removing the solvent in a conventional evaporator arrangement, and the resulting condensate can be reused. for example in a subsequent elution.
  • vanillin-containing crude product which optionally contains other low molecular weight constituents such as acetovanillon or vanillic acid and also if appropriate contains other constituents of the aqueous composition used, for example lignin.
  • any aqueous vanillin-containing compositions having a basic pH can be used in the process according to the invention, the pH generally being above pH 9, frequently at least pH 10, in particular at least pH 12 and especially at least or above pH 13 is.
  • the concentration of vanillin in the aqueous vanillin-containing composition is typically in the range of 1 to 5000 mg / kg, especially 5 to 2000 mg / kg. In a specific embodiment, the concentration of vanlillin is in the range of 5 to 500 mg / kg and especially in the range of 10 to 250 mg / kg. In another embodiment, the concentration of vanillin is in the range of 10 to 5000 mg / kg, and more preferably in the range of 20 to 2000 mg / kg.
  • the aqueous vanillin-containing compositions are typically liquids having a water content of generally at least 30% by weight, often at least 50% by weight, especially at least 60% by weight, based on the total weight of the composition. If the aqueous vanillin-containing compositions contain solids, it is possible to carry out filtration before treatment with the adsorbent, although this is not absolutely necessary.
  • aqueous, basic vanillin-containing composition is an aqueous, alkaline lignin-containing composition which, in addition to vanillin, lignin or lignin derivatives, for example lignin sulfate, lignin sulfonate, kraft lignin, alkali metal lignin , Sodalignin, or organosolv lignin or mixture thereof as lignin component and having an alkaline pH, usually at least pH 9, often at least pH 10, especially at least pH 12 and especially at least or above pH 13 having.
  • lignin or lignin derivatives for example lignin sulfate, lignin sulfonate, kraft lignin, alkali metal lignin , Sodalignin, or organosolv lignin or mixture thereof as lignin component and having an alkaline pH, usually at least pH 9, often at least pH 10, especially at least pH 12 and especially at least or above pH 13 having
  • the aqueous, alkaline lignin-containing composition generally contains from 0.5 to 30% by weight, preferably from 1 to 15% by weight, in particular from 1 to 10% by weight, of lignin, based on the total weight of the aqueous, lignin-containing composition.
  • the inventive method is particularly suitable for obtaining vanillin from aqueous, basic vanillin-containing compositions obtained by partial oxidation, especially by electrolysis, of an aqueous, alkaline lignin-containing suspension or solution.
  • the aqueous, alkaline lignin-containing suspension or solution used for the partial oxidation typically has a pH of at least pH 10, in particular of at least pH 12 and especially of at least or above pH 13.
  • the aqueous, alkaline lignin-containing suspension or solution used for the oxidation generally contains from 0.5 to 30% by weight, preferably from 1 to 15% by weight, in particular from 1 to 10% by weight, of lignin, based on the total weight of the aqueous, lignin-containing composition
  • the aqueous, alkaline solution or suspension used for the partial oxidation may be an aqueous solution or suspension which is obtained as a by-product in a technical process, such as pulp, cellulose or cellulose production, e.g. Black liquor, as well as the lignin-containing wastewater streams from the sulfite process, from the sulfate process, from the organocell or organosolv process, from the ASAM process, from the kraft process or from the natural pulping process.
  • the alkaline aqueous solution or suspension for oxidation may be an aqueous solution or suspension prepared by dissolving a lignin or lignin derivative in aqueous alkali, e.g.
  • bases for adjusting the pH of the aqueous, alkaline lignin-containing suspension or solution especially inorganic bases may be used, e.g.
  • Alkali metal hydroxides such as NaOH or KOH, ammonium salts such as ammonium hydroxide and alkali metal carbonates such as sodium carbonate, e.g. in the form of soda. Preference is given to alkali metal hydroxides, in particular NaOH and KOH.
  • concentration of inorganic bases in the aqueous, lignin-containing suspension or solution should not exceed 5 mol / L, in particular 4 mol / L, and is typically in the range from 0.01 to 5 mol / L, in particular in the range from 0.1 to 4 minor.
  • the partial oxidation of the aqueous, alkaline lignin-containing suspension or solution can be carried out in a manner known per se, e.g. according to the methods described in the cited prior art, in particular by controlled oxidation with atmospheric oxygen at elevated temperature in the presence of suitable transition metal catalysts, e.g. Copper or cobalt catalysts (see
  • the electrode materials used for the electrolysis can under the known for these purposes electrode materials such as nickel, silver, RuO x TiO x mixed oxides, platinized metals such as platiniert.es titanium or platinized niobium, platinum, graphite or carbon, but also under so-called base alloys, such as Ni base alloys, Co base alloys, Fe base alloys, Cu base alloys or Ag base alloys.
  • base alloys such as Ni base alloys, Co base alloys, Fe base alloys, Cu base alloys or Ag base alloys.
  • base alloys has not been described in the prior art for this purpose and is the subject of a parallel patent application.
  • the electrodes used in the electrolysis, or at least the anodes consist of an electrode material which comprises Co-base alloys, Fe-base alloys, Cu-base alloys, Ag-base alloys and Ni-base alloys and especially Co and Ni-base alloys is selected.
  • a base alloy is understood to mean an alloy which contains at least 50% by weight, in particular at least 55% by weight, especially at least 58% by weight, for example 50 to 99% by weight, preferably 50 to 95% by weight.
  • the total amount of all other alloying constituents other than the base metal being typically at least 1% by weight, in particular at least 5% by weight and especially at least 10% by weight and, for example, in the range from 1 to 50% by weight, preferably in the range from 5 to 50% by weight, in particular in the range from 5 to 45% by weight.
  • % more preferably in the range of 10 to 45 wt .-% and especially in the range of 10 to 42 wt .-%, all figures in wt .-% are each based on the total weight of the alloy.
  • Typical other alloy constituents are above all Cu, Fe, Co, Ni, Mn, Cr, Mo, V, Nb, Ti, Ag, Pb and Zn, but also Si, Accordingly, C, P and S are preferred.
  • Base alloys containing at least one other of the foregoing alloying constituents other than the base metal are preferred.
  • Preferred, in particular with regard to their stability and at the same time good selectivity are Ni-base alloys, Fe base alloys and Co base alloys, in particular Ni base alloys and Co base alloys.
  • Preferred, in particular with regard to their selectivity and at the same time satisfactory stability are Cu base alloys and Ag base alloys.
  • Typical nickel-base alloys are essentially, i. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight
  • b1) from 5 to 50% by weight, in particular from 5 to 45% by weight, particularly preferably from 10 to 45% by weight and especially from 10 to 42% by weight of at least one further alloying constituent selected from among Cu, Fe, Co, Mn, Cr, Mo, W, V, Nb, Ti, Si, Al, C and S.
  • Ni-base alloys particular preference is given to those which contain 5 to 35% by weight, in particular 10 to 30% by weight, of Cu as further alloying constituent. These alloys are referred to below as Group 1 .1.
  • the base alloys of group 1.1 may contain one or more of the following alloying ingredients in an amount of up to 45% by weight, in particular up to 40% by weight: Fe, Co, Mn, Cr, Mo, W, V, Nb, Ti, Si, Al, C and S.
  • Examples of Ni base alloys of group 1.1 are alloys of the EN short designations NiCu30Fe (Monel 400) and NiCu30AI as well as the Ni-Cu alloy of the following composition: 63% by weight.
  • Ni-base alloys 30 wt% Cu, 2 wt% Fe, 1.5 wt% Mn, 0.5 wt% Ti (Monel 500K).
  • Ni-base alloys particular preference is given to those which contain 5 to 40% by weight, in particular 15 to 30% by weight, of Cr as a further alloying constituent. These alloys are referred to below as group 1 .2.
  • the base alloys of group 1 .2 can contain one or more of the following alloying constituents in an amount of up to 40% by weight, in particular up to 35% by weight: Fe, Co, Mn, Cu, Mo, W, V, Nb, Ti, Si, Al, C and S.
  • Ni-base alloys of group 1 .2 are particularly preferred those which Mo, Nb and / or Fe as a further alloying ingredient, in particular a total amount of 1 to 30 wt .-%, contain.
  • Examples of Ni-base alloys of group 1 .2 are alloys of the EN-abbreviations NiCr19NbMo (Inconel® alloy 718) and NiCr15Fe (Inconel® alloy 600), NiCr22Mo19Fe5 (Inconel® 625), NiMo17Cr16FeWMn (Hastelloy® C276), a Ni-Cr-Fe alloy with a nickel content of 72-76 wt%, a Cr content of 18 to 21 Wt .-%, a C content of 0.08-0.13 wt .-% and an Fe content of 5 wt .-% and a Ni-Cr-Co-Mo alloy with a nickel content of 48 to 60 wt .-%,
  • Ni-base alloys particular preference is given to those which contain 5 to 35% by weight, in particular 10 to 30% by weight, of Mo as a further alloying constituent. These alloys are referred to below as Group 1.3.
  • the base alloys of group 1.3 may contain one or more of the following alloying ingredients in an amount of up to 40% by weight, in particular up to 35% by weight: Fe, Co, Mn, Cu, Cr, W, V, Nb, Ti, Si, Al, C and S.
  • the Ni base alloys of group 1.3 particular preference is given to those which contain Cr, Nb and / or Fe as a further alloy constituent, in particular in a total amount of from 1 to 30% by weight. %, contain.
  • Examples of Group 1 .3 Ni base alloys are alloys of the EN short names NiMo28 (Hastelloy® B and Hastelloy® B-2) and NiMo29Cr (Hastelloy® B-3).
  • Typical cobalt base alloys are essentially, i. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight of:
  • b1) from 5 to 50% by weight, in particular from 5 to 45% by weight, particularly preferably from 10 to 45% by weight and especially from 10 to 42% by weight of at least one further alloying constituent selected from among Cu, Fe, Ni, Mn, Cr, Mo, W, V, Nb, Ti, Si, P and C.
  • Co-base alloys particular preference is given to those which are 5 to
  • the base alloys of group 2.1 may contain one or more of the following alloy constituents in an amount of up to 40% by weight, in particular up to 35% by weight: Fe, Ni, Mn, Cu, Mo, W, V, Nb, Ti, Si, C and P.
  • the Co base alloys of group 2.1 particular preference is given to those which contain Mo, W and / or Fe as a further alloying constituent, in particular an amount of in total 1 to 30% by weight, contain.
  • Examples of Group 2.1 Co-base alloys are alloys of the compositions:
  • Typical iron-based alloys are high-alloy stainless steels. They usually consist essentially of, d. H. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight of:
  • b1) from 5 to 50% by weight, in particular from 5 to 45% by weight, particularly preferably from 10 to 45% by weight and especially from 10 to 42% by weight of at least one further alloying constituent selected from among Cu, Co, Ni, Mn, Cr, Mo, W, V, Nb, Ti, Si, P, S and C.
  • chromium-containing stainless steels are particularly preferred which contain Cr as alloy constituent in addition to the base metal, the chromium content generally being in the range from 5 to 30% by weight, in particular from 10 to 25% by weight.
  • group 3.1 the base alloys of group 3.1 may contain one or more of the following alloying ingredients in an amount of up to 40% by weight, in particular up to 35% by weight: Co, Ni, Mn, Cu, Mo, V, Nb, Ti, Si, C, S and P.
  • Fe base alloys of group 3.1 preference is given in particular to those which contain Ni, Mo, V, Ti, Si and / or Nb as a further alloying constituent, in particular a total of 1 to 30 wt .-%, contained.
  • Group 3.1 Fe base alloys are chromium steels, e.g. X12C 3, X6Cr17 and X20C 3, chromium-nickel steels, e.g.
  • chromium molybdenum steels eg X12Cr
  • Typical copper base alloys generally consist essentially of d. H. at least 95% by weight and in particular at least 98% by weight and especially at least 99% by weight
  • Examples of group 3.1 Cu base alloys are nickel silver (alloy of 62 wt.% Cu, 18 wt.% Ni and 20 wt.% Zn) and cupronickel (alloy of 75 wt.% Cu and 25 wt .-% Ni).
  • any type of electrode known to the person skilled in the art can be used as the anode.
  • This may consist entirely of the respective electrode material or be a carrier electrode having an electrically conductive carrier which is coated with the electrode material.
  • the electrodes used as the anode may, for example, be electrodes in the form of expanded metals, nets or sheets.
  • any electrode known to the person skilled in the art and suitable for the electrolysis of aqueous systems can be used as the cathode. Since reduction processes take place at the cathode and the lignin is oxidized at the anode, the loading of the vanillin with this heavy metal is so low when using a heavy metal electrode such as a nickel cathode that the vanillin obtained can be used without problems in the food industry.
  • the electrode materials exhibit a low hydrogen overvoltage.
  • the electrode material of the cathode is selected from Ni-base alloys, Co-base alloys, Fe-base alloys, Cu-base alloys, more preferably Ni-base alloys, Co-base alloys and Fe-base alloys and especially among the base alloys of groups 1 .1 , 1 .2, 1.3, 2.1 and 3.1.
  • any type of electrode known to the person skilled in the art can be used as the cathode.
  • This may consist entirely of the respective electrode material or be a carrier electrode having a carrier which is coated with the electrode material.
  • electrodes which consist of the respective electrode material in particular of one of the abovementioned base alloys, especially one of the base alloys of groups 1.1, 1.2, 1.3, 2.1 and 3.1.
  • the Thode used electrodes may be, for example, electrodes in the form of expanded metals, nets or sheets.
  • the arrangement of anode and cathode is not limited and includes, for example, arrangements of planar gratings and / or plates, which may also be arranged in the form of several, alternately polarized stacks and cylindrical arrangements of cylindrically shaped networks, grids or pipes, which are also in Form of several, alternately polarized cylinder can be arranged.
  • various electrode geometries are known to the person skilled in the art.
  • the anode and cathode can be separated by a separator.
  • the separator is typically a porous sheet placed between the electrodes, eg a grid, mesh, fabric or non-woven, of an electrically non-conductive material which is inert under the electrolysis conditions, eg a plastic material, in particular a Teflon material or a Teflon coated plastic material.
  • any electrolysis cells known to those skilled in the art may be used, such as divided or undivided flow cell, capillary gap cell or plate stack cell.
  • the undivided flow cell for example a flow cell with circulation, in which the electrolyte is continuously circulated past the electrodes.
  • the process can be carried out with good success both batchwise and continuously.
  • the electrolysis can also be carried out on an industrial scale.
  • Corresponding electrolysis cells are known to the person skilled in the art. All embodiments of this invention relate to both the laboratory and industrial scale.
  • the content of the electrolytic cell is mixed.
  • any mechanical stirrer known to those skilled in the art can be used.
  • the use of other mixing methods such as the use of Ultraturrax, ultrasound or jet nozzles is also preferred.
  • the current densities at which the process is carried out are generally 1 to 1000 mA cm 2 , preferably 1 to 100 mA / cm 2 .
  • the process according to the invention is particularly preferably carried out at current densities between 1 and 50 mA / cm 2 .
  • the total duration of the electrolysis naturally depends on the electrolytic cell, the electrodes used and the current density. The expert can determine an optimal duration by routine experiments, eg by sampling during the electrolysis.
  • the polarity can be changed at short intervals.
  • the polarity reversal can take place in an interval of 30 seconds to 10 minutes, an interval of 30 seconds to 2 minutes is preferred.
  • the anode and cathode are made of the same material.
  • the electrolysis is usually carried out at a temperature in a range of 0 to 160 ° C, preferably 50 to 150 ° C, wherein anodes of the aforementioned base alloys allow the electrolysis at lower temperatures, without a loss of selectivity occurs.
  • the electrolysis is then preferably carried out at temperatures in the range of 10 to 100 ° C, in particular in the range of 50 to 95 ° C and especially in the range of 70 to 90 ° C.
  • the electrolysis is usually carried out at a pressure below 2000 kPa, preferably below 1000 kPa, in particular below 150 kPa, e.g. in the range of 50 to 1000 kPa, especially 80 to 150 kPa performed. It is particularly preferred to carry out the process according to the invention at a pressure in the range of atmospheric pressure (101 ⁇ 20 kPa).
  • the particular advantages of the invention are particularly noticeable when the basic vanillin-containing composition is prepared by oxidation, in particular by electrolysis, of an aqueous, alkaline lignin-containing suspension or solution and vanillin formed during the oxidation during the oxidation thereof resulting basic vanillin-containing composition is removed or depleted by treatment of the basic vanillin-containing composition with the adsorbent.
  • This will reduce over-oxidation of vanillin. gert and the yield of vanillin, based on lignin used, can be significantly increased.
  • Removal or depletion of the vanillin from the aqueous-alkaline reaction mixture obtained during the oxidation can take place at intervals or continuously.
  • the oxidation of the aqueous, alkaline lignin-containing suspension or solution is interrupted, and the resulting aqueous alkaline reaction mixture is treated in the manner described above with the adsorbent, in particular the anion exchanger.
  • a stream of the aqueous-alkaline reaction mixture obtained during the oxidation from the oxidation reactor for example, is generally discharged.
  • an electrolysis cell treats the stream with the adsorbent, in particular with the anion exchanger and returns the vanillin depleted in this way stream in the oxidation reactor.
  • reaction products were carried out by gas chromatography.
  • the stationary phase used was an HP-5 column from Agilent with a length of 30 m, a diameter of 0.25 mm and a thickness of 1 ⁇ m. This column was heated by means of temperature program within 10 min at a heating rate of 10 ° C / min from 50 ° C to 290 ° C. This temperature was held for 15 minutes.
  • the carrier gas used was hydrogen at a flow rate of 46.5 mL / min.
  • Amberlite® IRA402 (OH) from Dow: OH form of a crosslinked styrene / divinylbenzene copolymer with Tnmethylammonium phenomenon bound via Ch in the form of gel-like particles (20 to 25 mesh) with a moisture content of 50 to 60%.
  • the anion exchanger has a capacity of 1, 2 meq / mL, based on a water-swollen bed of anion exchanger, or 4.1 meq / g, based on solids (about 1, 3 meq / ml in the chloride form) , Vertellius Specialties Reillex® HPQ (Sigma Aldrich): Cl-form of a cross-linked poly-4-vinylpyridine quaternized with methyl chloride and in the form of gel-like particles (particle size 300-1000 ⁇ ) with a moisture content of 55%.
  • the anion exchanger has a capacity of 4.1 meq / g based on solids.
  • Dowex Monosphere 550A OH from Dow OH form of a crosslinked styrene / -
  • the anion exchanger has a capacity of 1.0 meq / mL, based on a water swollen bed of the anion exchanger.
  • Ambersep 900 OH from Rohm & Haas (now Dow): OH form of a crosslinked styrene / divinylbenzene copolymer with trimethylammonium groups bonded via CH 2 in the form of gel-like particles (20 to 25 mesh) with a moisture content of 65%.
  • the anion exchanger has a capacity of 0.8 meq / mL, based on a water-swollen bed of the anion exchanger.
  • Amberlite® IRA910 (CI) from Dow: Cl-form of a crosslinked styrene / divinylbenzene copolymer with dimethyl 2-hydroxyethylammonium groups bonded via CH 2 in the form of macroporous particles (16 to 50 mesh) with a moisture content of 52%.
  • the anion exchanger has a capacity of 1, 0 meq / mIL based on a water-swollen bed of the anion exchanger, or 3.8 meq / g, based on solids on.
  • the dry resin was allowed to swell in 450 mL of methanol / H 2 O 2: 1 for 1 day and then filtered off.
  • the dry resin was allowed to swell in 450 mL of methanol / H 2 O 2 for 1 day and then filtered off.
  • the electrolysis was carried out analogously to Example 1 with the following change:
  • the work-up is carried out analogously to Example 1.
  • the filtrate obtained in this way was admixed with 100 ml of H 2 O and extracted three times with 150 ml of dichloromethane each time.
  • the combined organic phases were saturated with approx. 100 mL.
  • vanillin 50 mg were dissolved in 50 ml of 1 M aqueous sodium hydroxide solution in a screw-cap jar and mixed with 1 g of ion exchange resin previously for about 18 hours in distilled water. Water was swollen, offset. The suspension was shaken for 45 minutes at about 300 rpm, then filtered through a frit and rinsed twice with 10 ml of water.
  • the anion exchanger was filtered off from the basic solution of vanillin via a frit and transferred from the frit into a screw cap glass with 20 ml of an acidic methanolic solution (90% methanol, 10% concentrated hydrochloric acid). The frit was then rinsed thoroughly with dichloromethane. The suspension was again shaken for 45 minutes at about 300 rpm, filtered again through a frit, and this was rinsed thoroughly with about 15 mL of dichloromethane.
  • the filtrate was mixed with 2 ⁇ n-hexadecane and 30 mL of water, extracted 3 times with 30 mL dichloromethane, washed with 30 mL saturated brine and then dried over Na 2 SO 4 .
  • the solvent was removed under reduced pressure and the remaining light yellow solid was analyzed by gas chromatography.
  • the respectively recovered amount of vanillin from the two fractions (at least 95% of the originally used amount, ie> 47.3 mg) were determined from the gas chromatogram using the internal standard n-hexadecane.
  • Example 6 The procedure was carried out analogously to Example 6 using a solution of 49.2 mg of vanillin in 1 M NaOH (50 mL) and this with 1.02 g of ionausasucherharz (Dowex Monosphere 550a OH) and the suspension shaken for 1 h (frequency : 300 rpm). After washing with 10 mL of demineralized H2O, 20 mL of a 10% strength by weight solution of acetic acid in ethyl acetate and an additional 10 mL of ethyl acetate were added to the filtered-off ion exchange resin and shaken for 1 h (frequency: 300 rpm).

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Abstract

La présente invention concerne un procédé pour produire de la vanilline à partir d'une composition aqueuse basique contenant de la vanilline, notamment à partir d'une composition telle que celle obtenue lors de l'oxydation, notamment lors de l'oxydation par électrolyse, de compositions aqueuses alcalines contenant dans la lignine. Le procédé comprend au moins le traitement d'une composition aqueuse basique contenant de la vanilline, notamment le traitement d'une composition telle que celle obtenue lors de l'oxydation, notamment lors de l'oxydation par électrolyse, de compositions aqueuses alcalines contenant de la lignine, avec un adsorbant basique, notamment un échangeur d'anions.
EP13734066.7A 2012-07-04 2013-07-03 Procédé pour produire de la vanilline à partir de compositions aqueuses basiques contenant de la vanilline Withdrawn EP2870131A1 (fr)

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EP13734066.7A EP2870131A1 (fr) 2012-07-04 2013-07-03 Procédé pour produire de la vanilline à partir de compositions aqueuses basiques contenant de la vanilline

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WO2016071475A1 (fr) * 2014-11-07 2016-05-12 Basf Se Utilisation de 3,3'-diméthoxy-4,4'-dihydroxystilbène comme agent aromatisant
CN104532284A (zh) * 2014-12-16 2015-04-22 广西科技大学 一种在离子溶液中的电氧化水热木质纤维素转化方法及其装置
CN112205405B (zh) * 2020-11-11 2021-07-20 浙江新安化工集团股份有限公司 一种含有香草醛和精草铵膦类的除草组合物及除草剂
WO2023159017A1 (fr) * 2022-02-15 2023-08-24 Evolva Sa Procédé de récupération et de purification de vanilline
TWI794071B (zh) * 2022-04-01 2023-02-21 田寮生技數位科技股份有限公司 香草醛萃取及純化方法

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US2449364A (en) * 1945-10-15 1948-09-14 Hoffmann La Roche Process for isolating vanillin
GB615772A (en) * 1945-10-15 1949-01-11 Roche Products Ltd A process for isolating vanillin
CH245671A (de) 1945-10-15 1946-11-30 Hoffmann La Roche Verfahren zur Isolierung von Vanillin.
US2985589A (en) 1957-05-22 1961-05-23 Universal Oil Prod Co Continuous sorption process employing fixed bed of sorbent and moving inlets and outlets
US4277626A (en) * 1980-01-24 1981-07-07 Forss Kaj G Method for the isolation of vanillin from lignin in alkaline solutions
GB8527960D0 (en) 1985-11-13 1985-12-18 Mini Agriculture & Fisheries Electro chemical treatment of lignins
FR2617845B1 (fr) * 1987-07-09 1989-12-01 Organocell Zellstoff Umwelttec Procede de traitement de lignines en vue de l'obtention d'aldehydes et/ou d'acides phenoliques
KR100726204B1 (ko) 2000-03-29 2007-06-11 아처 다니엘 미드랜드 캄파니 발효 브로쓰로부터 염기성 아미노산을 분리하는 방법
US7649199B2 (en) * 2008-04-11 2010-01-19 Eastman Kodak Company N-type semiconductor materials in thin film transistors and electronic devices
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