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WO1999021810A1 - Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine - Google Patents

Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine Download PDF

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Publication number
WO1999021810A1
WO1999021810A1 PCT/EP1998/006622 EP9806622W WO9921810A1 WO 1999021810 A1 WO1999021810 A1 WO 1999021810A1 EP 9806622 W EP9806622 W EP 9806622W WO 9921810 A1 WO9921810 A1 WO 9921810A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
starting materials
heated
acid
aldehydes
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.)
Ceased
Application number
PCT/EP1998/006622
Other languages
German (de)
English (en)
Inventor
Olaf Gille
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.)
Individual
Original Assignee
Individual
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 to HU0004752A priority Critical patent/HUP0004752A2/hu
Priority to CA002309141A priority patent/CA2309141A1/fr
Priority to JP2000517923A priority patent/JP2001521013A/ja
Priority to PL98340311A priority patent/PL340311A1/xx
Priority to EP98952719A priority patent/EP1027310A1/fr
Priority to BR9813160-5A priority patent/BR9813160A/pt
Priority to KR1020007004663A priority patent/KR20010031612A/ko
Priority to EA200000466A priority patent/EA200000466A1/ru
Application filed by Individual filed Critical Individual
Priority to AU10307/99A priority patent/AU1030799A/en
Publication of WO1999021810A1 publication Critical patent/WO1999021810A1/fr
Priority to NO20002259A priority patent/NO20002259L/no
Anticipated expiration legal-status Critical
Priority to BG104479A priority patent/BG104479A/xx
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
    • C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
    • 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

Definitions

  • the invention relates to a process for the preparation of phenols, aldehydes, esters and / or ketones using lignin and / or ligninsulphonic acid, the lignin or the ligninsulphonic acid-containing starting materials from which the desired substance evaporates being heated.
  • DE 40 36 922 AI describes a method for removing pollutants from the exhaust air of a kiln. It indicates the possibility of recycling the collected and separated pollutants.
  • the invention has for its object to provide a method of the type described above, which works particularly economically.
  • this object is achieved in that the starting materials containing the lignin or the lignin sulphonic acid are heated, while usable products are produced from the solid constituents of the starting materials under the action of heat, with the emergence of the desired substance promoting boundary conditions which are observed for the Manufacture the usable products from the solid components of the raw materials are unusual but harmless.
  • the invention couples the production of phenols, aldehydes, esters and / or ketones using lignin and / or ligninsulphonic acid to the production of usable products from the solid, i.e. H. non-volatile constituents of the raw materials.
  • these products can be wood fiber boards or moldings, chipboard, insulation material or ceramic firing material.
  • ceramic firing material the invention differs from the prior art according to DE 40 36 922 AI, however, in that a larger range of substances can be produced from the lignin or the lignosulphonic acid by setting certain boundary conditions, or the desired substances by this supporting conditions to a much larger relative extent.
  • lignin or ligninsulphonic acid is generally also contained in the starting materials and is heated during the production of the products.
  • the proportion of lignin or lignin sulphonic acid that can be converted to produce the chemical substances can be increased.
  • special boundary conditions are set under which the lignin or lignin sulphonic acid is heated.
  • the specific boundary conditions are unusual compared to the usual manufacture of usable products and are, in themselves, unrealistic. However, it is easily possible to choose the boundary conditions so that they are harmless to the quality of the usable products.
  • the starting materials can contain lignin, ligninsulphonic acid, dry ligninsulphonic acid and / or ligninsulphonic acid condensate in order to provide the lignin or the ligninsulphonic acid for the production of the desired substances.
  • Lignin is known to be a component of wood. Lignin sulphonic acid is obtained when vacuuming off cellulose fibers, for example, in paper manufacture. It is known to add lignin sulphonic acid to the starting materials in the production of ceramic firing material but also, for example, in the production of chipboard.
  • phenols are to be produced in the process according to the invention, a reducing to neutral environment for the lignin or the lignin sulphonic acid must be set. Furthermore, the starting materials should not be heated for longer than 30 minutes to prevent oxidation of the phenols.
  • Lewis bases it is also important that the lignin or lignin sulphonic acid is heated in the absence of Lewis bases to produce phenols. It is not sufficient to only consider Lewis bases in the sense of a narrow chemical definition. Rather, all substances that could act as Lewis bases when the phenols are oxidized must be observed. This further term of the Lewis bases is also based on the following explanations.
  • a neutral to slightly oxidizing environment for the lignin or lignin sulphonic acid must be set, and the starting materials should be heated to a temperature of at least 100 ° C for more than 15 minutes.
  • an oxidizing environment for the lignin or lignin sulphonic acid has to be set, and the starting materials have to be heated to a temperature of over 120 ° C. for more than 25 minutes.
  • the lignin or ligninsulphonic acid can be heated in the presence of a Lewis base.
  • a strongly oxidizing environment for the lignin or the lignin sulphonic acid has to be set.
  • the starting materials should be heated to a temperature of over 140 ° C for more than 25 minutes. The heating should take place in the presence of a strong Lewis base.
  • boundary conditions for producing the individual desired substances always overlap to a certain extent.
  • a lower temperature range is always passed through before a higher temperature range is set.
  • a mixture of chemical substances always evaporates from the raw materials.
  • the selected boundary conditions make it possible to predominantly obtain the desired substances. In any case, it is advisable to prepare the mixture of substances evaporating from the raw materials in order to maintain the individual substances in good purity.
  • Processes for the production of solid products which are particularly suitable for coupling to the production of phenols, aldehydes, esters and / or ketones according to the present invention, are characterized in that in the vicinity of the starting materials, the temperature rises to above 250 ° C. takes place within such a long period of time that the desired substances are formed and can evaporate from the starting materials.
  • an ambient temperature of 250 ° C is not identical to a reaction temperature for the lignin or lignosulphonic acid of 250 ° C. This means that only the desired reaction temperatures of about 80 to 160 ° C. are achieved in the solid products.
  • processes for the production of the solid products in which the oxygen content of the environment of the starting materials can be adjusted are particularly suitable to have an influence on the chemical reaction, through which the lignin or lignin sulphonic acid is converted into the desired chemical substances.
  • microwave radiation does not only shorten the heating of the raw materials for the production of the usable products, which is already being used in a targeted manner in some technical areas. Microwave radiation also accelerates the chemical reactions important for the invention, as the reaction products of which the desired phenols, aldehydes, esters and / or ketones are obtained.
  • microwave radiation is suitable, as is also used in household appliances in so-called microwave devices. The wavelength of this microwave radiation is adapted to the optimal heating of water molecules. In the invention, microwave radiation with other wavelengths can also be used in order to specifically increase the yield of certain desired substances.
  • Microwave radiation is suitable for accelerating the reactions of interest here such that even when using pure lignin and without the presence of Lewis bases, even ketones can be obtained within comparatively short periods of time. After only 5 minutes. after the heating of the starting materials begins, the first desired substances emerge. This time is almost 120 min. Warm-up time for a conventional heating of large-volume moldings from the starting materials comparable.
  • the positive effect of microwave radiation in the invention can also be attributed to the selective excitation of certain starting materials, so that the microwave radiation acts as a catalyst for the desired reactions.
  • the environment of the lignin or ligninsulphonic acid should be neutral to slightly oxidizing.
  • the use of a light Lewis base supports the reaction of the phenols, which are first-order pyrolysis products of the lignin sugar molecules used, to the aldehydes.
  • the reaction time is at least about 20 minutes at at least 100 ° C.
  • esters Even more oxidizing boundary conditions must be observed than in the production of aldehydes.
  • a catalytically active substance e.g. B. a Lewis base
  • the reaction time is at least about 30 minutes.
  • the boundary conditions for the production of ketones are quite similar to those for the production of esters. But there are additionally set higher temperatures and even more oxidizing boundary conditions. For example, strong Lewis bases can be used as catalysts. Longer reaction times are also necessary. These reaction times should be at least about 30 minutes and the reaction temperature should be above 140 ° C.
  • wood fiber products such as molded parts and boards
  • wood fiber products are produced in different densities using different process control. Different by-products specific to these process points can be tapped at the different process points without the production of the main product being impaired.
  • phenols and aldehydes in particular can be obtained from the adhesive within the first 30 minutes of the manufacturing process. This is done by simply extracting the air at the respective process points. By compressing the substances obtained in this way and possibly by additional heating, parts of the phenols can be oxidized to aldehydes and parts of the aldehydes to esters.
  • the recovery of usable substances takes place here analogously to the production of wood fiber products.
  • the thermal insulation materials can take on the catalytic properties of Lewis bases and shift the reaction equilibrium in the direction of aldehydes, esters and ketones.
  • reaction time of less than 30 minutes and in the absence of catalytically active substances
  • more than 90% of substances already contained in the starting materials can be obtained and only very few reaction products are formed.
  • reaction time of significantly more than 30 minutes and in particular in the presence of catalytically active substances, i. H.
  • Substances that act as Lewis bases but are not necessarily Lewis bases in the sense of an exact chemical definition, produce up to 90% reaction products. This means that the recoverable substances are not already contained in the starting materials, but rather reaction products resulting from the starting materials.
  • the ceramic is generally not heated above 200 ° C. Depending on the temperature profile, different substances evaporating from the ceramic can be obtained. When the temperature rises slowly, phenols are primarily obtained. When using magnesite in the ceramic, the reaction equilibrium shifts towards the reaction products even at low temperatures, i. H. the aldehydes, esters and ketones, because magnesital already acts as a Lewis base even at low temperatures.
  • the rise in temperature can be greatly shortened by using microwave radiation.
  • the use of microwave radiation leads to a quasi-catalytic acceleration of the reactions, in particular pyrolysis reactions, as a result of which the desired substances are obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

L'invention concerne un procédé pour produire des phénols, des aldéhydes, des esters et/ou des cétones à l'aide de lignine et/ou d'acide sulfonique de lignine, dans lequel les matériaux de départ contenant la lignine ou l'acide sulfonique de lignine sont chauffés. La substance désirée est évaporée à partir de ces matériaux de départ, tandis que des produits valorisables sont fabriqués à partir des constituants solides des matériaux de départ sous l'action de la chaleur. A cet effet, sont respectées des conditions marginales favorisant la formation de la substance souhaitée, lesquelles sont anormales mais inoffensives pour la fabrication des produits valorisables issus des constituants solides des matériaux de départ.
PCT/EP1998/006622 1997-10-29 1998-10-20 Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine Ceased WO1999021810A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
KR1020007004663A KR20010031612A (ko) 1997-10-29 1998-10-20 리그닌 과/또는 리그닌 술폰산으로부터의 페놀, 알데히드,에스테르 와/또는 케톤의 제조방법
JP2000517923A JP2001521013A (ja) 1997-10-29 1998-10-20 リグニンおよび／またはリグニンスルホン酸からフェノール類、アルデヒド類、エステル類および／またはケトン類を製造する方法
PL98340311A PL340311A1 (en) 1997-10-29 1998-10-20 Method of obtaining phenoles, aldehydes, esters and/or ketons from lignin and/or lignosulphonic acid
EP98952719A EP1027310A1 (fr) 1997-10-29 1998-10-20 Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine
BR9813160-5A BR9813160A (pt) 1997-10-29 1998-10-20 Processo para a produção de fenóis, aldeìdos, ésteres e/ou cetonas a partir de lignina e/ou ácido sulfÈnico de lignina
HU0004752A HUP0004752A2 (hu) 1997-10-29 1998-10-20 Eljárás fenolok, aldehidek, észterek és/vagy ketonok előállítására ligninből és/vagy ligninszulfonsavból
CA002309141A CA2309141A1 (fr) 1997-10-29 1998-10-20 Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine
EA200000466A EA200000466A1 (ru) 1997-10-29 1998-10-20 Способ получения фенолов, альдегидов, сложных эфиров и/или кетонов из лигнина и/или лигнинсульфокислоты
AU10307/99A AU1030799A (en) 1997-10-29 1998-10-20 Method for producing phenols, aldehydes, esters and/or ketones from lignin and/or lignin sulphonic acid
NO20002259A NO20002259L (no) 1997-10-29 2000-04-28 FremgangsmÕte ved fremstilling av fenoler, aldehyder, estere og/eller ketoner av lignin og/eller ligninsulfonsyre
BG104479A BG104479A (en) 1997-10-29 2000-05-29 Method for producing phenols, aldehydes, esters and/or ketones from lignin and/or ligninsulphonic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19747688A DE19747688A1 (de) 1997-10-29 1997-10-29 Verfahren zur Herstellung von Phenolen, Aldehyden, Estern und/oder Ketonen aus Lignin und/oder Ligninsulphonsäure
DE19747688.0 1997-10-29

Publications (1)

Publication Number Publication Date
WO1999021810A1 true WO1999021810A1 (fr) 1999-05-06

Family

ID=7846944

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/006622 Ceased WO1999021810A1 (fr) 1997-10-29 1998-10-20 Procede pour la production de phenols, d'aldehydes, d'esters et/ou de cetones a partir de lignine et/ou d'acide sulfonique de lignine

Country Status (16)

Country Link
EP (1) EP1027310A1 (fr)
JP (1) JP2001521013A (fr)
KR (1) KR20010031612A (fr)
CN (1) CN1283171A (fr)
AU (1) AU1030799A (fr)
BG (1) BG104479A (fr)
BR (1) BR9813160A (fr)
CA (1) CA2309141A1 (fr)
DE (1) DE19747688A1 (fr)
EA (1) EA200000466A1 (fr)
HU (1) HUP0004752A2 (fr)
NO (1) NO20002259L (fr)
PL (1) PL340311A1 (fr)
TR (1) TR200001197T2 (fr)
WO (1) WO1999021810A1 (fr)
YU (1) YU24900A (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2935393B1 (fr) 2008-08-29 2012-08-24 Tetrahedron Bacteries et levures enrichies en selenium organique a partir de composes seleno-hydroxyacides et leurs applications en nutrition, cosmetique et pharmacie
FR2935394B1 (fr) 2008-08-29 2013-03-08 Eco Solution Microorganismes photosynthetiques enrichis en selenium organique a partir de composes seleno-hydroxyacides et leurs applications en nutrition, cosmetique et pharmacie
CN103508871B (zh) * 2013-10-25 2015-06-17 东南大学 一种黑液木质素液相降解制取4-羟基-3-甲氧基苯基乙酮的方法
CN105541559B (zh) * 2016-01-24 2018-08-10 东北石油大学 钙钛矿类氧化物催化木质素生产芳香基含氧化合物的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2547913A (en) * 1948-06-16 1951-04-03 Aschaffenburger Zellstoffwerke Process for the preparation of vanillin and vanillin derivatives
US5034498A (en) * 1989-07-19 1991-07-23 Biocarbons Corporation Method and apparatus for producing water-soluble resin and resin product made by that method
WO1996009350A1 (fr) * 1994-09-19 1996-03-28 Midwest Research Institute Procede de preparation de composes phenoliques a partir de lignines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4036922A1 (de) * 1990-11-20 1992-05-21 Olaf Gille Verfahren und vorrichtung zum entfernen von schadstoffen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2547913A (en) * 1948-06-16 1951-04-03 Aschaffenburger Zellstoffwerke Process for the preparation of vanillin and vanillin derivatives
US5034498A (en) * 1989-07-19 1991-07-23 Biocarbons Corporation Method and apparatus for producing water-soluble resin and resin product made by that method
WO1996009350A1 (fr) * 1994-09-19 1996-03-28 Midwest Research Institute Procede de preparation de composes phenoliques a partir de lignines

Also Published As

Publication number Publication date
TR200001197T2 (tr) 2000-10-23
EA200000466A1 (ru) 2000-10-30
EP1027310A1 (fr) 2000-08-16
CN1283171A (zh) 2001-02-07
DE19747688A1 (de) 1999-05-06
NO20002259L (no) 2000-06-21
KR20010031612A (ko) 2001-04-16
BG104479A (en) 2001-02-28
PL340311A1 (en) 2001-01-29
BR9813160A (pt) 2000-08-22
AU1030799A (en) 1999-05-17
NO20002259D0 (no) 2000-04-28
YU24900A (sh) 2002-09-19
HUP0004752A2 (hu) 2001-04-28
JP2001521013A (ja) 2001-11-06
CA2309141A1 (fr) 1999-05-06

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