EP2276877A1 - Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode - Google Patents
Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrodeInfo
- Publication number
- EP2276877A1 EP2276877A1 EP09745700A EP09745700A EP2276877A1 EP 2276877 A1 EP2276877 A1 EP 2276877A1 EP 09745700 A EP09745700 A EP 09745700A EP 09745700 A EP09745700 A EP 09745700A EP 2276877 A1 EP2276877 A1 EP 2276877A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- diamond electrode
- vanillin
- derivatives
- 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.)
- Granted
Links
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 Conife- ren wood and 22 wt .-% in hardwood.
- Lignin is considered to be a higher molecular weight derivative of phenylpropane. Depending on the type of wood, the phenyl ring is substituted with one to two methoxy groups and the propane units with hydroxy groups. In softwoods the predominantly guaiacyl type is found, in hardwood also the syringyl and coumar type. Lignan and coumarin structures, cyclic ethers and lactones are also formed by various linking possibilities.
- Alkali lignin is used in North America as a binder for wood and cellulosic press plates, as a dispersing agent, for clarifying sugar solutions, stabilizing asphalt emulsions and stabilizing foams.
- 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 describes the electrochemical cleavage of lignin for obtaining vanillin and its derivatives, such as guaiacol and acetovanillon (3-methoxy-4-hydroxyacetophenone).
- vanillin and its derivatives such as guaiacol and acetovanillon (3-methoxy-4-hydroxyacetophenone).
- work is carried out in aqueous alkaline solution, wherein heavy metal electrodes are used.
- the work-up is carried out 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.
- EP 0245418 B1 causes vanillin or its derivatives to be used as phenolic compounds. lat or hydroxybenzaldehyde derivatives are present. However, the phenolates or hydroxybenzaldehyde derivatives of vanillin and vanillin derivatives are very sensitive to oxidative processes which are to take place in an alkaline medium. For the workup, a neutralization must therefore be carried out beforehand, so that an increased workup effort is necessary to obtain vanillin.
- This object is achieved by a process for the degradation of lignin with a higher yield than 5 wt .-% of hydroxybenzaldehyde derivatives and / or phenol derivatives, wherein an aqueous solution or suspension of the lignin is electrolyzed on a diamond electrode.
- the process according to the invention is advantageous, the process being carried out in an aqueous solution which has a pH of ⁇ 11.
- the process of the invention is advantageous, in which case an aqueous, acidic solution is used.
- 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 is advantageous, the lignin degradation products being 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 in aqueous solution, wherein the aqueous solution is a pH of ⁇ 1 1, preferably ⁇ 9, particularly preferably acidic. Most preferably, the pH is ⁇ 3.
- the pH is adjusted to a pH ⁇ 3 with readily water-soluble inorganic acids 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 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. 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 diademantel 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 can be used which have been produced by the chemical vapor deposition (CVD) method. Such electrodes are commercially available, such as from the manufacturer: Condias, Itzehoe; Diaccon, Hundth (Germany) or Adamant Technologies, La-Chaux-de-Fonds (Switzerland).
- HTHP-BDD electrodes are commercially available from pro aqua, Niklasdorf (Austria) and their properties are described by A Cieciwa, R. Wüthrich and Ch. Comninellis in Electrochem. Commun. 8 (2006) 375-382.
- 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 in short time 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 at boron-doped diamond electrodes can be increased by the addition of additives such as TiC "2.
- TiC" 2 is preferably used in catalytic amounts.
- a metal-containing or metal-free redox mediator may be added, preferably 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 electrolysed at a current density of 80 mA / cm 2 and a temperature of 30 0 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 shows the following typical composition (GC area percentages): 27% guaacol, 24% vanillin, 24% acetovanillon and 25% other compounds.
- the stationary phase used was a dB1 column from J & W Scientific with a length of 30 m and a diameter of 0.25 mm and a layer thickness of 1 ⁇ m. This column is heated by means of a temperature program of 80 0 C within 5 min in 8 ° C steps to 250 0 C.
- the carrier gas used is helium at a flow rate of 20 to 30 mL / min.
Landscapes
- 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)
Description
Claims
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 true EP2276877A1 (de) | 2011-01-26 |
EP2276877B1 EP2276877B1 (de) | 2011-11-09 |
Family
ID=41055312
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09745700A Not-in-force EP2276877B1 (de) | 2008-05-14 | 2009-05-11 | Verfahren zur elektrochemischen spaltung von lignin an einer diamantelektrode |
Country Status (9)
Country | Link |
---|---|
US (1) | US20110089046A1 (de) |
EP (1) | EP2276877B1 (de) |
JP (1) | JP2011521102A (de) |
CN (1) | CN102027161B (de) |
AT (1) | ATE532888T1 (de) |
BR (1) | BRPI0912164A2 (de) |
CA (1) | CA2722235A1 (de) |
RU (1) | RU2495157C2 (de) |
WO (1) | WO2009138368A1 (de) |
Families Citing this family (12)
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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2005014887A1 (ja) * | 2003-08-08 | 2005-02-17 | Ebara Corporation | 液中電極およびその材料 |
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 |
-
2009
- 2009-05-11 JP JP2011508877A patent/JP2011521102A/ja active Pending
- 2009-05-11 BR BRPI0912164A patent/BRPI0912164A2/pt not_active IP Right Cessation
- 2009-05-11 CN CN2009801172252A patent/CN102027161B/zh not_active Expired - Fee Related
- 2009-05-11 EP EP09745700A patent/EP2276877B1/de not_active Not-in-force
- 2009-05-11 US US12/992,217 patent/US20110089046A1/en not_active Abandoned
- 2009-05-11 CA CA2722235A patent/CA2722235A1/en not_active Abandoned
- 2009-05-11 RU RU2010150834/04A patent/RU2495157C2/ru not_active IP Right Cessation
- 2009-05-11 WO PCT/EP2009/055638 patent/WO2009138368A1/de active Application Filing
- 2009-05-11 AT AT09745700T patent/ATE532888T1/de active
Non-Patent Citations (1)
Title |
---|
See references of WO2009138368A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE532888T1 (de) | 2011-11-15 |
US20110089046A1 (en) | 2011-04-21 |
RU2010150834A (ru) | 2012-06-20 |
EP2276877B1 (de) | 2011-11-09 |
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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