EP2132377A1 - Procédé d'extraction de lignine - Google Patents

Procédé d'extraction de lignine

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Publication number
EP2132377A1
EP2132377A1 EP08706378A EP08706378A EP2132377A1 EP 2132377 A1 EP2132377 A1 EP 2132377A1 EP 08706378 A EP08706378 A EP 08706378A EP 08706378 A EP08706378 A EP 08706378A EP 2132377 A1 EP2132377 A1 EP 2132377A1
Authority
EP
European Patent Office
Prior art keywords
lignin
radical scavenger
radical
group
molecules
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Withdrawn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
EP08706378A
Other languages
German (de)
English (en)
Inventor
Tobias Voitl
Philipp Rudolf Von Rohr
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.)
Eidgenoessische Technische Hochschule Zurich ETHZ
Original Assignee
Eidgenoessische Technische Hochschule Zurich ETHZ
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
Application filed by Eidgenoessische Technische Hochschule Zurich ETHZ filed Critical Eidgenoessische Technische Hochschule Zurich ETHZ
Publication of EP2132377A1 publication Critical patent/EP2132377A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials

Definitions

  • the present invention relates to the targeted conversion of lignin to chemicals.
  • Lignin is a major component of plants that provide rigidity to the cell scaffold.
  • the lignin content can vary from plant to plant.
  • the chemical structure of lignin also has plant-specific differences.
  • the macromolecule lignin depending on the plant type of different
  • Vanillin is the only lignin-based phenolic product that is commercially produced. Part of the global production of vanillin (12,000 tonnes / year) is achieved by oxidative degradation of lignosulfonic acids.
  • the invention takes into account in two respects the chemically complex task of maximizing the yield of degradation products.
  • the reaction of lignin is carried out in the presence of a catalytic system.
  • This catalytic system includes so-called polyoxometalates, which allows the selective cleavage of bonds even at relatively low temperatures.
  • radical scavengers are added to the reaction mixture. These prevent repolymerization reactions, or combination reactions of lignin fragments, and stabilize the desired target products.
  • the alkaline oxidation of lignin can be used.
  • the reaction of 10 g of a hardwood lignin (steam digestion) under 1.4 MPa oxygen and 170 ° C using a Cu (II) / Fe (III) catalyst results in 4.7 wt% vanillin and 9.5 wt% syringaldehyde.
  • the yield of aldehydes vanillin and syringaldehyde was 15% by weight.
  • Various polyoxometalates have been used for delignification and patented, as described, for example, in US 5,302,248, US 5,552,019 or WO95 / 26438.
  • the unbleached pulp is treated here in a first process step with an aqueous polyoxometalate solution (eg: Na 7 AlVW 11 O 4 Q) under an inert atmosphere, wherein the lignin is finally converted to carbon dioxide and water.
  • an aqueous polyoxometalate solution eg: Na 7 AlVW 11 O 4 Q
  • the invention thus aims to convert lignin directly into chemicals by means of polyoxometalates.
  • so-called free-radical scavengers can be used in addition to polyoxometalates.
  • lignin and polyoxometalates each describe whole classes of substances and are therefore briefly presented below.
  • chemicals can be obtained from all lignin types using the method described in this invention. It is also possible to carry out a targeted pretreatment of the lignin used, for example to modify the solubility in organic or inorganic solvent. It is also possible to use an already partially decomposed lignin.
  • lignin-containing biomass such as wood
  • Polyoxometallates belong to the class of metal-oxygen cluster anions. Polyoxometalates are characterized, among others, by their mostly simple synthesis, their structural modification and their specific redox behavior. For many reaction systems important key properties, such as solubility in organic / inorganic media, redox potential and pH, can be adapted by targeted synthesis.
  • the synthesis of the polyoxometalates is usually carried out in one stage by heating an acidic, aqueous solution containing all the components in the desired, stoichiometric ratio. The polyoxometalate, or the Polyoxometalatmischung, thus resulting from the amounts of the components used. It also makes it clear that there is a wide variety of polyoxometalates. The following two names for structurally different polyoxometalates have become established in the literature: "isopolyanions" and "heteropolyanions”. These anions are represented by the following general empirical formula:
  • polyoxometalates includes both anion types: isopoly and heteropolyanions.
  • heteropolyacids are very strong acids, which are composed of heteropolyanions with protons as countercations. In the case that all countercations consist of other elements, one also speaks of heteropoly salts. A number of these polyoxometalates have proven to be particularly interesting for catalysis.
  • M molybdenum or tungsten
  • X Heteroatoms
  • P 5+ , Si 4+ , As 5+ , Ge 4+ , B 3+ are most frequently mentioned in connection with catalytically used polyoxometalates.
  • P 5+ , Si 4+ , As 5+ , Ge 4+ , B 3+ are most frequently mentioned in connection with catalytically used polyoxometalates.
  • polyoxometalates In comparison to the very large number of polyoxometalates, only a few polyoxometalates are currently used as catalysts, these being mainly limited to the class of keggin anions and their derived structures. It is therefore usually sufficient to use a very simplified nomenclature.
  • heteroatoms are placed in front of the addenda atoms and the countercations in front of the heteroatoms.
  • the heteropolyanion is placed in square brackets and thus separated from the countercations.
  • Na 6 [P 2 Mo 1S O 62 ] can thus be represented as [P 2 Mo 18 O 62 ] or even P 2 Mo 18 .
  • Any polyoxometalate (isopoly and heteropolyanions), its acids, salts and partial salts can be used regardless of the method of preparation of this invention. It is also possible to use mixtures of different polyoxometalates. In fact, depending on the pH in solution, many species may be in equilibrium side by side, with a crystalline isolated compound not necessarily being the major component.
  • the polyoxometalates used can be reversibly oxidized and reduced, which is the case for all polyoxometallates of the Keggin and Wells / Dawson type.
  • a preferred class of polyoxometalates are components of the form [Y 3-1S] 0+ [X 1-4 M 1-36 O O 1 -60] 11 ", each" X "released from the elements of the
  • Periodic system is selectable and / or also a molecular part with four or less
  • each "X” is chosen freely from the group of elements P, Si, As, Ge, B, Al, Co, S 5 Fe.
  • Each "M” part is preferably free Mo, W, V, Ti 3 Co, Cu, Zn, Fe, Ni, Mn, Cr, lanthanides, Ce, Al, Ga, In, Tl.
  • the counter cations "Y" are preferably free from the group H.
  • polyoxometalates of Form [Yf + [XM 12 O 40 ] 11 ' where "Y", “X", “M” and “n” are the same definitions as above, the most preferred polyoxometalates are of the form [Yf + [ XM 12 O 40 ] " " , wherein "Y” and “n” are as defined above, "X” is Si, P, Ge or As and each "M” is freely selected from Mo, V or W.
  • one or more components are used as Radikallanger.
  • Radical scavengers serve in the context of this invention to scavenge the radicals formed during the degradation of lignin and thus to reduce repolymerization reactions. In particular, this should increase the yield of desired chemicals.
  • Radical scavengers are generally all components which, under the given conditions, form radicals in one or more steps or already exist as free radicals.
  • radical scavengers which are already present as free radicals in the form S *.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
  • radical free radical polymerization as radical scavenger.
  • radical scavengers which can form free radicals by homolytic cleavage of a covalent bond (Equation 4). From a thermodynamic point of view, a relatively low binding energy of the S-S 'bond in comparison to the binding energies of the possible coupling products R-S, R'-S, R-S' and R'-S 'is then to be preferred when selecting the radical scavenger.
  • free radical scavengers which are free radicals in several steps form.
  • several steps can be taken in conjunction with catalysts to form a radical S *.
  • S * For example, acid-catalyzed condensation of methanol to dimethyl ether in the presence of POM as an acid catalyst with subsequent homolytic cleavage of the ether bond to the radicals CH 3 O * and CH 3 'drove.
  • the radical scavenger can serve as a hydrogen donor and, on the other hand, prevent the repolymerization of the lignin fragments.
  • suitable components of the general form S-H are those in which H represents a hydrogen available for reaction and S denotes the radical of the radical scavenger, i. minus the considered hydrogen atom.
  • the radical scavenger can have several accessible hydrogen atoms.
  • radical scavenger The operation of the radical scavenger is illustrated in the following exemplary second reaction scheme.
  • radicals which have been formed by separation of an ether bond of the lignin (equation 5), where R in turn represents lignin fragments, are now considered.
  • radicals of the form R * (or S *) in the presence of oxygen form radicals of the form ROO * (or SOO *). Due to the sometimes very strong tendency of POMs to pick up electrons (and protons), POM can also interact with radical scavengers. It should be noted at this point that phenolic degradation products of lignin are per se radical scavengers.
  • radical scavengers molecules which can give off hydrogen atoms under the given conditions are suitable as radical scavengers. Therefore, considering the chemical structure, H 2 is the simplest radical scavenger. Also possible are alcohols and acids.
  • molecules are prepared which contain at least one benzene ring in their structure.
  • molecules are produced which have at least one and at most three benzene rings in their structure.
  • Most preferred is an embodiment in which molecules are made containing only one benzene ring in their structure.
  • the benzene ring is used as a backbone used.
  • the functional groups and possible bonds between Benzqlringen can be chosen arbitrarily.
  • the radical scavengers which may be used can be integrated into the structure of the chemicals produced. It is possible to obtain a mixture of several chemicals by the method explained in this invention.
  • One embodiment provides for converting lignin into a suitable reactor by means of POM.
  • lignin and POM are dissolved or suspended in a suitable liquid medium.
  • the mixture is placed on conditions which promote the degradation of lignin for a sufficient time.
  • the temperature may be between 0 ° C and 500 0 C, but preferably between 25 ° C and 300 ° C.
  • the degradation of lignin can take place here under inert gas, oxygen-containing, ozone-containing or hydrogen-containing gas at pressures up to 300bar.
  • the pH value can be in the range 0-10 or be set.
  • products from the group of chemicals defined above are to be formed.
  • the products are obtained in the range between complete decomposition of lignin and quasi-unchanged lignin.
  • This approach represents a new optimization task in terms of suitable POM systems, temperatures, reaction times, etc.
  • the difficult task of intercepting degradation products can be solved, inter alia, by the use of radical scavengers.
  • One embodiment therefore envisages converting lignin by means of POM in the presence of radical scavengers.
  • This procedure is analogous to the first embodiment.
  • the main difference is that at a suitable time a radical scavenger is added to the reaction mixture.
  • the radical scavenger can be present as a solid, liquid or gas.
  • Radical scavengers are generally all components which under the given conditions form radicals in one or more steps or are already present as free radicals.
  • scavengers for example, substances can be used which can give off one or more hydrogen atoms under the conditions used.
  • POM can promote the activation of radical scavengers (or the formation of radicals) due to their mostly strong electron (and proton) affinity.
  • radical scavengers It is also possible to use stable radicals, such as nitroxyl radicals, as radical scavengers. It is also possible to use radical formers, such as, for example, dibenzoyl peroxide from the group of peroxides, as radical scavengers.
  • Another embodiment provides to convert lignin by means of POM in the presence of two liquid phases.
  • the procedure is analogous to the first embodiment.
  • the main difference is that two only partially or immiscible liquid phases are in contact during the degradation of lignin. Due to different solubilities of POM, lignin and lignin-based degradation products in the selected liquid phases, a partial or complete separation of the components lignin, POM and lignin-based degradation products can take place.
  • a further embodiment provides to convert lignin by means of POM in the presence of radical scavengers and two liquid phases.
  • a further embodiment provides for using a metallic catalyst in conjunction with one of the abovementioned embodiments.
  • Combinations of metallic catalysts, mostly palladium, with polyoxometalates have been studied in a number of oxidations and reductions.
  • Catalyst allows the degradation of lignin at lower temperatures and has a positive effect on the selectivity of the target products. It is also the case that the yield of desired products using an additional increase metallic catalyst. It is possible to use a metallic catalyst in combination with polyoxometalates for the most complete oxidation of non-desired degradation products of lignin during the workup.
  • reaction stage The reaction of lignin according to the above-mentioned embodiments (reaction stage). Separation of the products from the reaction medium (for example by extraction).
  • non-target lignin fragments or lignin for energy production (e.g., thermal energy from oxidation).
  • the essence of the invention is thus inter alia, in summary, a process for the direct production of molecules having a minimum molecular weight of 78 g / mol by the degradation of lignin, lignin derivatives, lignin fragments and / or lignin-containing substances or mixtures in the presence of at least one polyoxometalate in a liquid medium.
  • a radical scavenger is preferably used at least in sections, during the degradation, wherein this radical scavenger is preferably a system or a mixture of systems which contains radicals, such as e.g. atomic hydrogen provides and / or which the repolymerization resp.
  • radicals such as e.g. atomic hydrogen provides and / or which the repolymerization resp.
  • the radical scavenger can be used gaseous, liquid and / or as a solid, and wherein the radical scavenger is particularly preferably selected from: molecular hydrogen, a peroxide such. Hydrogen peroxide or
  • Dibenzoyl peroxide an alcohol such as methanol and / or ethanol, a stabilized free radical such as a nitroxyl radical, an organic acid such as ascorbic acid, a phenol such as butylhydroxytoluene, an ether such as dimethyl ether, an ester such as ethyl acetate, an anhydride such as
  • Acetic anhydride or mixtures of such systems are Acetic anhydride or mixtures of such systems.
  • a second, liquid phase can be added to the mixture, wherein this second liquid phase preferably has a substantially different polarity from the first medium.
  • a metallic catalyst in particular from the group of transition-element-containing catalysts, preferably from the group VIIIB group of metal-containing and / or group IB metal-containing catalysts, it being possible for the catalyst to be bound to and / or in a preferably porous substrate ,
  • the reaction can be carried out under an inert gas, under an oxygen-containing gas phase, under a hydrogen-containing gas phase or under an ozone-containing gas phase in the pressure range from 0 to 300 bar, preferably at more than 5 bar.
  • the polyoxometalate is H 3 PMo 12 O 40 , in liquid medium to water, wherein an alcoholic radical scavenger is used, preferably selected from methanol and / or ethanol, wherein particularly preferably the volume ratio of water to alcoholic radical scavenger in the range of 1:10 to 10: 1 and wherein preferably a pressure of more than 2 bar prevails.
  • an alcoholic radical scavenger is used, preferably selected from methanol and / or ethanol, wherein particularly preferably the volume ratio of water to alcoholic radical scavenger in the range of 1:10 to 10: 1 and wherein preferably a pressure of more than 2 bar prevails.
  • the liquid medium is water, optionally in combination with an alcohol. It can be used per 100 ml of liquid medium between 2-200 g Polyoxometallate, more preferably between 8-12 g. It is therefore preferable to use concentrations in the range from 0.01 mol / 1 to 1 mol / l.
  • Fig. 1 shows chemicals from the degradation of lignin by means of POM and radical scavengers.
  • the liquid phase was removed after 20 minutes. The sampling was carried out by a water-cooled cooling coil. The sample was filtered once and then extracted three times with 10 ml of chloroform. To the organic phase was added 30 ⁇ l of n-decane as internal standard for GC / MS analysis (Fisons instruments GC8000 / MD800; column of Restek Rtx-5MS 30m x 0.25mm x 0.25 ⁇ m).
  • the yield of lignin-based products was increased by about 30% by in situ extraction (see Experiment 01 with Experiment 02).
  • a second liquid phase chloroform
  • chloroform was added to the reaction mixture. This has a higher solubility for the desired degradation products and can therefore any products formed the actual reaction medium (aqueous POM solution) withdraw before possible subsequent reactions destroy the products formed again.
  • the lignin from Aldrich (Batch NrO9724CE) is according to the manufacturer a softwood lignin (mainly from spruce wood), which was obtained by Kraft process.
  • the lignin from the Granit® process was obtained from agricultural plants and therefore has a different chemical structure.
  • the sodium salt Na 3 PMo 12 O 4 O corresponding to H 3 PMo 12 O 4O was used as POM.
  • the yield of chemicals is noticeably higher in this experiment. It therefore appears that, from a chemical point of view, minor changes in the POM system used can affect the yield of desired products. The use of an optimal POM system is therefore crucial for achieving high yields.
  • Figure 1 shows the associated GC / MS chromatograms and illustrates that not only are the amounts of vanillin and 4-hydroxyacetyl-2-methoxy-phenol produced greater when using the radical scavengers, but also new components are prepared in comparable amount to vanillin.
  • dimethyl ether as a radical scavenger to react lignin in aqueous H 3 PMo 12 O 40 solution under nitrogen and in the absence of methanol resulted in the production of a small amount of vanillic acid methyl ester. It has thus been shown that dimethyl ether is effective directly as radical scavenger and the homolytic cleavage of dimethyl ether and the associated formation of vanillic acid methyl ester is possible.
  • poplar lignin was used.
  • the product yield is also in the range of 3.5 wt .-%.
  • the main products here are vanillin (5.0mg), vanillic acid methyl ester (6.2mg), syringaldehyde (8.2mg) and syringic acid methyl ester (12.2mg), corresponding to the chemical structure of poplar lignin with a relatively high proportion of syringyl units.
  • vanillic acid methyl ester is formed when using methanol and ethyl vanillate when using Ethanol. It therefore appears possible, by means of suitable combinations of POM and free-radical scavengers, to be able to decisively influence not only the yield but also the selectivity with respect to a target product.
  • Table 1 Results for the preparation of chemicals from lignin using POM and radical scavenger compared to conventional methods. based on dry lignin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

L'invention concerne un procédé de fabrication directe de molécules ayant un poids moléculaire minimal de 78 g/mol par extraction de lignine, de dérivés de lignine, de fragments de lignine et/ou de matériaux ou mélanges contenant de la lignine, en présence d'un polyoxométallate et de préférence en présence d'un piège à radicaux, dans un fluide liquide.
EP08706378A 2007-03-02 2008-02-25 Procédé d'extraction de lignine Withdrawn EP2132377A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH3382007 2007-03-02
CH01595/07A CH702124B1 (de) 2007-03-02 2007-10-12 Verfahren zum Abbau von Lignin.
PCT/CH2008/000078 WO2008106811A1 (fr) 2007-03-02 2008-02-25 Procédé d'extraction de lignine

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EP2132377A1 true EP2132377A1 (fr) 2009-12-16

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US (1) US7906687B2 (fr)
EP (1) EP2132377A1 (fr)
JP (1) JP2010520157A (fr)
CN (1) CN101680167A (fr)
BR (1) BRPI0808430A2 (fr)
CA (1) CA2679854A1 (fr)
CH (1) CH702124B1 (fr)
WO (1) WO2008106811A1 (fr)

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WO2008106811A1 (fr) 2008-09-12
US20100121110A1 (en) 2010-05-13
JP2010520157A (ja) 2010-06-10
CN101680167A (zh) 2010-03-24
BRPI0808430A2 (pt) 2014-07-29
US7906687B2 (en) 2011-03-15
CH702124B1 (de) 2011-05-13
CA2679854A1 (fr) 2008-09-12

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