EP2276877B1 - Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode - Google Patents

Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode Download PDF

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Publication number
EP2276877B1
EP2276877B1 EP09745700A EP09745700A EP2276877B1 EP 2276877 B1 EP2276877 B1 EP 2276877B1 EP 09745700 A EP09745700 A EP 09745700A EP 09745700 A EP09745700 A EP 09745700A EP 2276877 B1 EP2276877 B1 EP 2276877B1
Authority
EP
European Patent Office
Prior art keywords
lignin
process according
diamond electrode
vanillin
diamond
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.)
Not-in-force
Application number
EP09745700A
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German (de)
English (en)
French (fr)
Other versions
EP2276877A1 (de
Inventor
Ulrich Griesbach
Andreas Fischer
Florian Stecker
Jörg Botzem
Ralf Pelzer
Mario Emmeluth
Siegfried R. Waldvogel
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BASF SE
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BASF SE
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Priority to EP09745700A priority Critical patent/EP2276877B1/de
Publication of EP2276877A1 publication Critical patent/EP2276877A1/de
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Publication of EP2276877B1 publication Critical patent/EP2276877B1/de
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Classifications

    • 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 invention relates to a process for the electrochemical cleavage of lignin by means of a diamond electrode and to a process for the preparation of vanillin and its derivatives by electrochemical cleavage of lignin in solutions having a pH ⁇ 11.
  • Lignin is a high molecular weight, aromatic substance that fills the spaces between the cell membranes in woody plants and turns them into wood.
  • the lignin content of the dried plant material is about 27 to 33 wt .-% in coniferous wood and 22 wt .-% in hardwood.
  • Lignin is considered to be a higher molecular weight derivative of phenylpropane.
  • the phenyl ring is substituted with one to two methoxy groups and the propane units with hydroxy groups.
  • softwoods there is mainly the guaiacyl type, in hardwood also the syringyl and coumar type.
  • lignan and coumarin structures, cyclic ethers and lactones are formed by various linking possibilities.
  • Alkali lignin is used in North America as a binder for wood- and cellulose-based press plates, as a dispersant, for the clarification of sugar solutions, for the stabilization of asphalt emulsions and for foam stabilization.
  • the alkali lignin is used as an energy source for the pulp process by burning the black liquors.
  • Vanillin is widely used as a flavoring for chocolate, confectionery, liquors, baked goods and other sweet foods, as well as vanillin sugar instead of expensive natural vanilla.
  • the vanilla content of wood which has been made into wine barrels, contributes to the flavoring of wine. Smaller amounts are used in deodorants, perfumes, and to improve the taste of pharmaceuticals and vitamin supplements.
  • Vanillin is also an intermediate in the synthesis of various drugs, e.g. L-dopa, methyldopa and papaverine.
  • EP-B 0 245 418 is the electrochemical cleavage of lignin for the recovery of vanillin and its derivatives such as guaiacol and acetovanillon (3-methoxy-4-hydroxyacetophenone) described.
  • vanillin and its derivatives such as guaiacol and acetovanillon (3-methoxy-4-hydroxyacetophenone) described.
  • work is carried out in aqueous alkaline solution, wherein heavy metal electrodes are used. Work up is done using toxic organohalogen solvents such as chloroform. From the (eco) toxicological point of view, this is very disadvantageous, as is the use of heavy metal electrodes.
  • the use of high sodium hydroxide concentrations, as in EP 0245418 B1 describes vanillin or its derivatives as phenolate or Hydroxybenzaldehydderivate present.
  • This object is achieved by a process for the degradation of lignin with a higher yield than 5 wt .-% of Hydroxybenzaldehydderivaten and / or phenol derivatives, wherein an aqueous solution or suspension of lignin is electrolyzed on a diamond electrode and is operated in an aqueous solution, the has a pH ⁇ 11.
  • the process of the invention is advantageous, working in an aqueous, acidic solution.
  • the method according to the invention wherein the diamond electrode used is a boron-doped diamond electrode.
  • the inventive method wherein the Ligninabbau area are continuously removed from the electrochemical cell.
  • the inventive method wherein the Ligninabbau area be removed by continuous extraction with an organic solvent.
  • the process according to the invention wherein the lignin degradation products are selected from the group of guaiacol, vanillin and acetovanillon.
  • the lignin used for degradation is any lignin known to those skilled in the art.
  • it is lignin contained in products selected from the group of straw, bagasse, black liquor, kraft lignin, lignin sulphonate, organosolv lignin, and related papermaking or fiberwood residues.
  • Particularly preferred is the starch lignin and the lignin containing lignin sulphonate.
  • the hydroxybenzaldehyde derivatives and / or phenol derivatives resulting from the degradation of lignin can be obtained by the process according to the invention to more than 5% by weight.
  • the hydroxybenzaldehyde derivatives and / or phenol derivatives resulting from the degradation of the lignin are selected from the group of guaiacol, vanillin and acetovanillon. Particularly preferred are vanillin or guaiacol.
  • the Hydroxybenzaldehydderivate and / or phenol derivatives obtained by the process according to the invention can be continuously removed from the reaction products.
  • these Hydroxybenzaldehydderivate and / or phenol derivatives are removed from the reaction mixture by distillation or extraction continuously.
  • Particularly preferred is the steam distillation.
  • the lignin is present in aqueous solution, the aqueous solution having a pH of ⁇ 11, preferably ⁇ 9, particularly preferably being acidic.
  • the pH is particularly preferably ⁇ 3.
  • the pH is preferably adjusted to a pH ⁇ 3 with inorganic acids which are readily soluble in water, such as hydrochloric acid, sulfuric acid, nitric acid or organic acids such as para-toluenesulfonic acid or mixtures of various acids. Particularly preferred is sulfuric acid.
  • any electrolysis cell known to those skilled in the art can be used, such as divided or undivided flow cell, capillary gap cell or plate stack cell. Particularly preferred is the undivided flow cell. To achieve optimum space-time yields, a bipolar arrangement of several electrodes is advantageous.
  • the anode is a diamond electrode.
  • These diamond electrodes contain a diamond layer applied to a carrier material, wherein the carrier material is selected from the group of niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic carriers such as titanium suboxide. Particular preference is given to niobium or silicon as support material.
  • the diamond layer on the carrier may be doped with other elements. Boron- or nitrogen-doped diamond electrodes are preferred. Particularly preferred are boron-doped diamond electrodes.
  • any conventional low oxygen overpotential cathode material selected from the group consisting of RuO x TiO x mixed oxide electrode (DSA), platinized titanium, platinum, nickel, molybdenum or stainless steel may be used.
  • DSA RuO x TiO x mixed oxide electrode
  • the use of boron- or nitrogen-doped diamond electrodes is particularly preferred. Very particular preference is boron-doped diamond electrodes.
  • diamond electrodes which have been prepared by the CVD method (chemical vapor deposition).
  • Such electrodes are commercially available, such as from the manufacturer: Condias, Itzehoe; Diaccon, Hundth (Germany) and Adamant Technologies, La-Chaux-de-Fonds (Switzerland).
  • HTHP-BDD electrodes are commercially available from pro aqua, Niklasdorf (Austria), their properties are from A Cieciwa, R. Wüthrich and Ch. Comninellis in Electrochem. Commun. 8 (2006) 375-382 described.
  • the temperature for the process according to the invention is between 20 and 150 ° C., preferably in the range from 90 to 120 ° C.
  • the current density is preferably in the range of 5 to 3000 mA / cm 2 , more preferably in the range of 10 to 200 mA / cm 2 .
  • the polarity can be changed at short intervals.
  • the polarity reversal can take place in an interval of 30 seconds to 10 minutes, preferably an interval of 30 seconds and 2 minutes.
  • the efficiency of the electrolysis of lignin in aqueous solution on boron-doped diamond electrodes can be increased by the addition of additives such as TiO 2 .
  • TiO 2 is preferably used in catalytic amounts.
  • a metal-containing or metal-free redox mediator may be added, transition-metal-free mediators, e.g. Nitrosodisulfonates such as Fremy's salt (dipotassium nitrosodisulfonate).
  • any mechanical stirrer known to those skilled in the art but also other mixing methods such as the use of Ultraturrax or ultrasound can be used.
  • a suspension of 30 g of kraft lignin in an electrolyte consisting of 570 g of dilute sulfuric acid (0.1 M), in an undivided cell, with an electrode stack of boron-doped diamond cathodes (expanded metal, 5 x 10 cm) and boron-doped diamond anodes (expanded metal, 5 x 10 cm) at a distance of 0.5 cm is electrolyzed at a current density of 80 mA / cm 2 and a temperature of 30 ° C for 1 hour with stirring at 9500 U / min.
  • the resulting cell voltage is in the range of 2-6 V.
  • the aqueous phase is extracted with methyl tert-butyl ether (MTBE), the solid is filtered off with suction and washed with MTBE.
  • the aqueous phase is extracted several times with MTBE, the organic phases are combined, dried and the solvent is removed.
  • the gas chromatographic analysis of the crude organic product gives the following typical composition (GC area percentages): 27% guaiacol, 24% vanillin, 24% acetovanillon and 25% other compounds.
  • a dB1 column from J & W Scientific 30 m in length and 0.25 mm in diameter and 1 ⁇ m in thickness, was used as the stationary phase. This column is heated by means of a temperature program of 80 ° C within 5 min in 8 ° C steps to 250 ° C.
  • the carrier gas used is helium at a flow rate of 20 to 30 mL / min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Compounds Of Unknown Constitution (AREA)
EP09745700A 2008-05-14 2009-05-11 Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode Not-in-force EP2276877B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09745700A EP2276877B1 (de) 2008-05-14 2009-05-11 Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08156190 2008-05-14
PCT/EP2009/055638 WO2009138368A1 (de) 2008-05-14 2009-05-11 Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode
EP09745700A EP2276877B1 (de) 2008-05-14 2009-05-11 Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode

Publications (2)

Publication Number Publication Date
EP2276877A1 EP2276877A1 (de) 2011-01-26
EP2276877B1 true EP2276877B1 (de) 2011-11-09

Family

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EP09745700A Not-in-force EP2276877B1 (de) 2008-05-14 2009-05-11 Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode

Country Status (9)

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US (1) US20110089046A1 (pt)
EP (1) EP2276877B1 (pt)
JP (1) JP2011521102A (pt)
CN (1) CN102027161B (pt)
AT (1) ATE532888T1 (pt)
BR (1) BRPI0912164A2 (pt)
CA (1) CA2722235A1 (pt)
RU (1) RU2495157C2 (pt)
WO (1) WO2009138368A1 (pt)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8853478B2 (en) 2008-09-08 2014-10-07 Basf Se Method for the integrated production of cellulose and low-molecular-weight reusable materials
CN102277591B (zh) * 2011-08-02 2014-03-05 北京化工大学 一种电化学方式降解木质素的方法
US8808781B2 (en) * 2011-08-11 2014-08-19 Basf Se Method for producing vanillin by electrochemical oxidation of aqueous lignin solutions or suspensions
BR112014032854A2 (pt) 2012-07-04 2017-06-27 Basf Se processo para a produção de vanilina a partir de uma composição aquosa básica compreendendo vanilina
US9006494B2 (en) 2012-07-04 2015-04-14 Basf Se Process for producing vanillin from vanillin-comprising compositions
CN104603329B (zh) 2012-07-04 2017-06-27 巴斯夫欧洲公司 制备香草醛的方法
CN103074639B (zh) * 2013-02-04 2015-04-29 河北工业大学 一种电化学降解木质素制备2,6-二叔丁基-4-甲基苯酚的方法
CN103469244B (zh) * 2013-08-02 2015-10-28 河北工业大学 硫酸亚铁溶液中电化学降解木质素制备邻苯二甲酸二丁酯的方法
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
CN106480472B (zh) * 2015-08-25 2019-03-12 中国科学院天津工业生物技术研究所 将生物质材料一步转化为可溶性物质的方法、容器及用途
AT518544B1 (de) * 2016-04-29 2017-11-15 Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg Verfahren zur elektrochemischen Konvertierung von in Reststoffen enthaltenen oder als Reststoffe anfallenden organischen Verbindungen und Verwendung einer einkammrigen als Durchflusszelle konzipierten Elektrolysezelle zur elektrochemischen Konvertierung von in Reststoffen enthaltenen oder als Reststoffe anfallenden organischen Verbindungen in einen gasförmigen Brennstoff
CN106987862B (zh) * 2017-04-12 2018-03-09 中北大学 一种在低共熔溶剂中电化学降解木质素的方法

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US372581A (en) * 1887-11-01 And ed
US370370A (en) * 1887-09-27 Camera-plate holder for holding negative-paper
JPS5121346A (en) * 1974-08-16 1976-02-20 Sanwa Chemical Co Ltd Parupukogyohaisuino datsushokujokahoho
GB8527960D0 (en) * 1985-11-13 1985-12-18 Mini Agriculture & Fisheries Electro chemical treatment of lignins
FR2730730B1 (fr) * 1995-02-20 1997-04-04 Rhone Poulenc Chimie Procede de preparation d'un 4-hydroxybenzaldehyde substitue
US6136186A (en) * 1997-01-31 2000-10-24 Lynntech, Inc. Photocatalytic oxidation of organics using a porous titanium dioxide membrane and an efficient oxidant
PT989181E (pt) * 1998-04-09 2010-06-15 Suntory Holdings Ltd Processo para a produção de óleos essenciais por tratamento com água supercrítica e óleos essenciais obtidos por tratamento com água supercrítica
JP2005060752A (ja) * 2003-08-08 2005-03-10 Ebara Corp 液中電極材料
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JP2006068617A (ja) * 2004-09-01 2006-03-16 Ebara Corp 水媒体の処理方法及び装置
DE102006034895A1 (de) * 2006-07-25 2008-01-31 Siemens Ag Verfahren zur Entfernung von Schadstoffen aus Flüssigkeiten und Vorrichtung zur Durchführung des Verfahrens

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Publication number Publication date
ATE532888T1 (de) 2011-11-15
US20110089046A1 (en) 2011-04-21
RU2010150834A (ru) 2012-06-20
EP2276877A1 (de) 2011-01-26
WO2009138368A1 (de) 2009-11-19
CA2722235A1 (en) 2009-11-19
CN102027161A (zh) 2011-04-20
JP2011521102A (ja) 2011-07-21
RU2495157C2 (ru) 2013-10-10
CN102027161B (zh) 2013-01-09
BRPI0912164A2 (pt) 2015-10-13

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