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WO2011061399A1 - Substance contenant de la lignine oxydée, utilisation de cette substance, et procédé de purification de fluides contaminés - Google Patents

Substance contenant de la lignine oxydée, utilisation de cette substance, et procédé de purification de fluides contaminés Download PDF

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Publication number
WO2011061399A1
WO2011061399A1 PCT/FI2010/050932 FI2010050932W WO2011061399A1 WO 2011061399 A1 WO2011061399 A1 WO 2011061399A1 FI 2010050932 W FI2010050932 W FI 2010050932W WO 2011061399 A1 WO2011061399 A1 WO 2011061399A1
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Prior art keywords
lignin
containing material
charged components
derivative
aqueous fluid
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PCT/FI2010/050932
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English (en)
Inventor
Peter Blomberg
Anna Kalliola
Original Assignee
Valtion Teknillinen Tutkimuskeskus
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Application filed by Valtion Teknillinen Tutkimuskeskus filed Critical Valtion Teknillinen Tutkimuskeskus
Priority to EP10831203.4A priority Critical patent/EP2501745A4/fr
Publication of WO2011061399A1 publication Critical patent/WO2011061399A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4837—Lignin
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the present invention relates to sorbents based on lignocellulosic materials.
  • the present invention concerns oxidized lignin-containing materials, derivatives made from lignin-containing material, methods of purifying aqueous fluids, methods of purifying solids permeable to aqueous fluids and to novel uses of lignin-containing material.
  • Plant carbohydrates cellulose, hemicelluloses and lignin are the most abundant biomass components on the planet. Due to the limited resources of fossil fuels and to the greenhouse effect there is a need for using renewable biomass as a source of energy.
  • a lignocellulose-to-ethanol process the lignocellulosic material is first pretreated either chemically or physically to make the cellulose fraction more accessible to hydrolysis. Methods known in the art include steam explosion, with or without chemicals, such as sulphuric acid, ammonia, etc., hot water treatment, mild acid hydrolysis, CaO treatment, wet oxidation, organic solvent treatment, ammonium treatment, etc. Lignin is then separated from the pretreated material using conventional methods. The cellulose fraction is hydro lysed to obtain sugars that can be fermented by yeast into ethanol. Also the paper industry uses corresponding pre-treatment methods before separating lignin from cellulosic fibres.
  • lignin is a low-value by-product, which typically is used as a solid fuel.
  • lignin derivatives have also found a number of applications.
  • compounds such as lignosulphonates or lignophosphonates can to some extent replace the use of synthetic sorption materials because they are generally negatively charged and provide numerous binding sites for positively charged compounds, especially for cationic metal ions.
  • the negative charge of the lignosulphonates and lignophosphonates stems essentially from sulphonic or phosphonic groups.
  • Lignophosphonates cause increased catalyst deactivation, increased slagging in boilers and they give rise to a phosphorous-rich ash which has very little use in the cement industry.
  • the ask has to be disposed of by landfills which, in turn, causes eutrophication of the water environment.
  • WO2005/012194 describes systems for air and water purification using charged sorbent mediums including also lignin, and methods for their use.
  • the publication generally concludes that lignin typically carries negative charge on its surface and can thus remove cationic compounds from aqueous phase.
  • Sud et al. (2008) discuss the use of agricultural waste material as a potential adsorbent for sequestering heavy metal ions from aqueous solutions.
  • an oxidized lignin-containing material such as oxidized lignin and derivatives thereof, capable of sorbing positively charged components, such as metal ions, from aqueous fluids, such as industrial effluents.
  • the present invention provides an oxidized lignin- containing material which exhibits a negative charge primarily due to carboxylic groups present on the material. It has been found that the sorbtive capacity of the material is surprisingly good and it can be used as a biosorbent. Typically, the charge of the material, based on the content of the carboxylic groups, is at least 500 ⁇ /g dry weight at pH 8. More specifically, the oxidized material according to the present invention is characterized by what is stated in the characterizing part of claim 1.
  • the invention also provides a process for removing charged compounds from aqueous fluids and is usable also for high amounts of material to be treated. Accordingly, according to a third aspect, the invention concerns a method of purifying an aqueous fluid containing charged components, comprising the steps of contacting the aqueous fluid with a sorbent comprising a lignin-containing material or a derivative thereof, and sorbing charged components having an opposite charge to that of the sorbent so as to effectively reduce the content of the charged components in the fluid.
  • the invention provides for purification of solids or solid materials permeable to aqueous fluid, which contain containing charged components.
  • aqueous fluid which contain containing charged components.
  • a sorbent comprising an oxidized lignin-containing material or a derivative thereof exhibiting a relatively high negative or positive charge to bind at least a part of the charged components.
  • the spent material is subjected to sequestering.
  • a further aim of the present invention is to provide biosorbents which have high carboxylic charge density, preferably at least 1 meq/g, more preferably at least 2 meq/g , more preferably at least 3 meq/g most preferably at least 4 meq/g at neutral pH.
  • high charge of sorbent results in high purification capacity of charged components.
  • a further object of the present invention is to provide biosorbents which can be easily regenerated to remove (hazardous) compounds, e.g., before combustion or use as a landfill material. After regeneration with acid, the hazard compounds can be recovered.
  • the present invention is based on the surprising finding that oxidized, essentially carboxyl- charged lignin-containing materials can be used as effective biosorbents for purifying industrial sludge, process streams, aqueous waste fluids, municipal waste waters, contaminated natural waters or any other aqueous fluid including paint residues from car industry.
  • the lignin- containing material described here is highly charged. Since the major charge stems from carboxylic acids, it is easy and safe to regenerate compared to lignosulphonates or lignophosphonates. It is essentially sulphur free and can thus be incinerated without an express need to purify the combustion gases.
  • carboxyl charged lignin- containing biosorbent has good pH and thermal stability. As such, oxidized lignin is negatively charged with carboxylic groups and usable, e.g., as biosorbent for positively charged components. Such material can be used for removing charged components from fluids by various mechanical implementations.
  • lignin can be separated by e.g. acid precipitation.
  • the lignin-based or lignin-containing sorbtion material can be used, e.g., as a crude filtrate or lignin precipitate obtained from pretreated bio mass or TMP-reject.
  • lignin precipitate means a lignin fraction that is separated after a pulping process or after pretreatment in bio fuel process.
  • the oxidized lignin- containing material is used as a sorbent for calcium in the same pulping process without precipitation.
  • the material is based on renewable sources and can be obtained as byproducts of processes for biorefming of cellulosic or hemicellulosic materials. Since such processes will, in the future, to an increasing extent be integrated with the pulp or paper production (integrated biorefmeries) and with lignocelluloses-to-fuel -processes, there will be an oversupply of separated lignin. For this reason, the present sorbent materials will be available at low-cost and in great abundance.
  • Figure 1 is a schematic presentation of principles of obtaining the carboxyl charged lignin- containing material.
  • Figure 2 is a graph showing the decrease in calcium as a function of addition of oxidized lignin-containing material or 0.005 M EDTA (reference).
  • An increase in the Ca 2+ concentration in the beginning of the experiment is a Ca electrode detection error due to the pH adjustment from 2 to 6.
  • Initial volume of calcium solution was 800 ml, amount of Ca 2+ was 100 ppm.
  • Figure 3 is a graph showing the decrease in calcium as a function of addition 0,005 M EDTA, 0,1 M NaOH (two parallel samples) and oxidized lignin-containing material.
  • Initial volume of calcium solution was 800 ml, amount of Ca 2+ was 100 ppm.
  • Figure 4 is a graphic depiction showing the decrease of Ca 2+ as a function of added EDTA (control) or oxidized lignin-containing material. Lignin samples were reveived by oxidation with copper catalyst (CatOx) and without a catalyst (AlkOx). Initial volume of calcium solution was 700 ml, amount of Ca 2+ was 100 ppm.
  • Figure 5 is a graph showing the pH of the solution as a finction of added oxidized lignin- containing material or 0.1 M EDTA. Lignin samples were reveived by oxidation with a copper catalyst (CatOx) and without a catalyst (AlkOx).
  • Figure 6 is a graph showing the decrease of calcium as a function added oxidized lignin- containing material added as a filtrate and given as added volumes.
  • Initial volume of Calcium solution was 200 ml
  • amount of Ca 2+ was 100 ppm
  • pH of the filtrate reweived by oxidation with a copper catalyst (CatOx) and withouh a catalyst (alkOx) was 4,1.
  • Figure 7 is a graph showing the decrease of calcium as a function added oxidized lignin- containing material given as dry solids.
  • Two filtrate samples (CatOx and AlkOx) have been tested in pH's 4,1 and 6,5.
  • Initial volume of Calcium solution was 200 ml, amount of Ca 2+ was 100 ppm.
  • Figure 8 is a graph showing the molecular weight distribution of material present in filtrates reveived by oxidation with a copper catalyst (CatOx) and without a catalyst (AlkOx). Definitions
  • the expressions "sorbent” and “sorbent material” signify a material that has a capacity to host charged contaminants, e.g., by adsorption or absorption.
  • the sorption can be based on any kind of interaction, including, but not limited to, coulombic attration (e.g. Donnan partitioning, ion exchange), and chemisorption (e.g. complexation, chelation). Regardless of the sorption mechanism, the expression covers all materials that can reduce the activity of the free form of a charged solute by an interaction to some but not all solutes.
  • biosorbent covers sorbent materials made from renewable biomass, essentially any lignocellulosic material except living cells. Such material may be for example a polyelectrolyte or chelate. Biosorbtion is generally a process in which material originating from renewable biomass is used for sorption.
  • Oxidized lignin refers to any lignocellulosic material treated with an oxygen-containing oxidizing agent or a fraction thereof. If made from a source containing native lignin, the oxidation will convert most, or at least part, of the aromatic substructures into carboxyl- containing constructions.
  • the "carboxyl charged" lignin can be obtained by any method capable of achieving oxidation of the phenolic groups to corresponding carboxylic acids.
  • agents that can be employed in oxidation are any oxygen containing agents such as C"2, ⁇ 2 0 2 and organic peroxides.
  • the expressions "carboxyl charged” and "essentially carboxyl charged” are used synonymously and mean that most of, or at least some, of the charge of the material stems from carboxylic acids.
  • Known charged lignin-based materials include lignosulphonates and lignophosphonates.
  • this invention concerns lignin material where the major ionizable functional group comes from carboxylic groups.
  • an amphoteric material i.e., one having both negative and positive charges, is covered with the expression. It is to be understood that other components, such as hemicelluloses, have an effect on the net charge of lignin-containing material.
  • Preferably at least 50 % of the charge at pH 8 stems from carboxylic groups, more preferably 70 %, and most preferably 90 %.
  • lignin-containing material means any plant derived material including lignin and/or oxidation products thereof.
  • Examples of lignin-containing materials are crude filtrate obtained from pretreatment and lignin precipitate obtained from said filtrate. Lignin-containing material exists both in filtrate and precipitate. Half of the dry matter in the titrate is lignin. Most of the precipitate is lignin-containing material.
  • One purpose of this invention is to provide an oxidized lignin-containing material to lower the activity of positively charged components in aqueous fluids, thus acting as a biosorbent.
  • This invention is directed especially to sorption of positively charged compounds in aqueous fluids.
  • Sorption of an impurity may include any kind of taking and holding of an impurity, possibly by the actions of absorption or adsorption or a combination thereof.
  • the biosorbent consist essentially of lignin.
  • Lignin can be obtained as a low- value by-product from pulping and bio fuel, especially bioethanol, processes. It is renewable and safe to handle, use and recycle.
  • the biosorbents further contain cellulosic and hemicellulosic components. There is no need to separate lignin from other plant derived materials but usually lignin is deemed a waste product and is separted due needs of e.g. pulping process or hydrolysis to sugars for fermentation.
  • the lignin-containing biosorbent is an oxidized filtrate of pulping process.
  • the charged lignin- containing material is an oxidized material from a bio fuel process.
  • the oxidized lignin- containing material has a negative charge of at least 500 ⁇ Qq/g per dry weight at pH 8.
  • the net charge can be measured e.g. by quantifying the adsorptive capability of select divalent ions like Ba 2+ at pH 8.
  • the net charge is defined as the positive charge less the negative charge, completely ignoring any small counterions.
  • the net charge may also be synonymous with the amount of carboxylic moieties, including derivatives of the same.
  • the negative charge of lignin- containing material at neutral pH stems mainly from carboxylic groups.
  • neutral pH means a pH between 4 and 10, preferably between 5 and 9 and most preferably between 6 and 8.
  • the pKa of carboxylic acids range from 2 to 6, largely depending on the electron density of the atoms in their vicinity.
  • An isolated and non-interacting carboxylic acid group has a pKa of about 4.
  • the oxidative degradation of lignin usually creates carboxylic acid moieties close to each other, which typically alter their pKa values.
  • the close interaction between formed carboxylic acids and remaining aromatic structures also alter the pKa values.
  • Carboxylic acids have a negative charge at pH values above their pKa value. This means that the material has maximum adsorptive capability at pH values above 5, where all carboxylic acids are readily available for sorption. At pH near the pKa, some of the acid groups tend to be protonized and the metal ion needs to compete with the proton for the carboxylate groups. With pKa values spread out over a range of pH values, the ionic charge and therefore the sorptive capability, is not abruptly lost at one specific pH, but only reduced. It is also true that partial regeneration can be made if the pH of the regeneration solution is not below all pKa values within the material. Considering that there are chemically different sorption sites, evidenced by the differing pKa values, some sites may preferentially bind some metal ions. It has not been investigated, but the selective regeneration may have limited use in metal separation.
  • the carboxyl oxidized lignin is obtained by process as described in WO2009/034325, the content of which is herewith incorporated by reference.
  • the lignocellulo lytic raw-material is treated in alkaline aqueous medium in the presence of a catalyst and dioxygen.
  • Catalyst may be a transition metal catalyst comprising copper coordinated with at least one aliphatic or aromatic nitrogen donor ligand.
  • the carboxyl oxidized lignin is obtained by process as described in WO2009/034325 but catalyst is not used.
  • the carboxyl oxidized lignin is obtained by suspending a sample into a solution of 26.5 g/L (0.25 mol/L) Na 2 CC"3 and stirring under 10 atm 0 2 pressure and kept at 120 °C for 20 hours.
  • the carboxyl charged oxidized lignin is obtained from pulping process where lignocellulo lytic mass is pretreated in order to seprate lignin before paper manufacturing process.
  • the carboxyl charged oxidized lignin is obtained from process where lignocellulo lytic mass is pretreated before mass hydrolysis to provide sugars for fermentation. If necessary, the lignin-containing material can be further oxidized. Cellulosic fraction and carbohydrates are preferably separated or fermented to yield alcohol, that is then recovered.
  • the charged lignin material or charged lignin-containing material can be used as such as oxidation product (filtrate containg cellulose and soluble fraction of lignin and hemicellulases) or it can be isolated by conventional methods such as precipitation by acid.
  • the material is water soluble or soluble in other aqueous fluids.
  • the amount of carboxylic groups is at least 500 ⁇ /g, preferably over 2 mmol/g, and most preferably over 4 mmol/g.
  • the amounts are expressed per dry matter of the lignin.
  • the carboxyl charged material is chemically modified to have a net positive charge at pH 8.
  • the resulting material may be amphoteric.
  • a positive net charge allows the sorption of negatively charged components.
  • the net charge of a derivative may be more than 0.5 meq/g, prefereably more than 1 meq/g, and most preferably more than 2 meq/g. Higher charge results in enhanced capacity to purify the fluid from anionic compounds.
  • the lignin or lignin-containing material is functionalized by small organic molecules such as diamine compounds.
  • small organic molecules such as diamine compounds.
  • Such material is usable as biosorbent for anions depending the needs of purification.
  • the lignin or lignin-containing material is modified to have cationic charge and/or combined with another sorbtion material.
  • Positive charge may stem from e.g. amines or amides.
  • a carboxyl charged process filtrate containing lignin, hemicelluloses and alternatively cellulose is provided for use.
  • Charged lignin can function as a polyelectrolyte or as a chelate depending on its molecular size.
  • Both lignin and any lignin-containing material can be further fractionated into fractions with different molecular size distributions for use in various applications.
  • the size distributions affect the sorption properties of the materials and can therefore be more suitable for some applications.
  • the lignin-containing material or derivative thereof can be fractionated according to molecular weight and said fractions are used as polyelectrolytes or chelates allowing to optimize the sorbtion properties for each application.
  • Fractionating can be performed using conventional methods such as partial precipitation, filtration, kromatographic methods, dialysis or electrophoresis. Fractions with high molecular weight components ranging typically between 500 and 5000 Daltons (in practice up to even 150 kDa) are especially usable as polyelectrolyte applications whereas fractions having low molecular weight components ranging typically between 150 and 1000 Da have chelate characteristic. Filtrates containing suitable material for both applications can be obtained by oxidation process descibed in WO2009/034325; the oxidation can be conducted both with or without a catalyst. The average molecular weight (Mw) measured from the filtrates obtained with a copper catalyst (CatOx) was ca.
  • Fractions with high molecular weight molecules are suited for sedimentation and flocculation whereas fractions with fractions with chelating properties can be separated from the fluid by flocculation, sedimentation, filtration, centrifugation or flotation.
  • various fractions may have different tendency to colour the material to be treated.
  • Different fractions of lignin may be used for different applications: typically small molecules have characteristics of chelate and they remain in a soluble form also after sorbtion.
  • polyelectrolyte lignin-containing biosorbents are usable e.g. as a chelating agent, as a flocculant in water purifications, as thickener, emulsifier, conditioner, dispersion agent, as a filler in composites, as additive in soap, shampoo or other cosmetics, in a battery, in cement, or in oil recovery or chromatography.
  • a chelate can be removed from the treated aqueous solution by conventional methods such as flocculation, sedimentation, filtration, centrifugation or flotation.
  • the charged lignin fraction is akin to a polyelectrolyte, i.e. it has molecules with medium or high molecular weight of 1000 to 5000 Da and high charge density. It can be used for removing charged components, especially metal ions, such as divalent calcium ions from process water streams as a sorbent or an ion exchanger.
  • An embodiment of the invention is to provide a method of purifying an aqueous fluid containg charged components, comprising the steps of contacting the aqueous fluid with a sorbent comprising a ligning containing material or a derivative thereof as described here and sorbing charged components having an opposite charge to that of the lignin-containing material or the derivative thereof, respectively, to the sorbent in order to reduce the content of said oppositely charged components in the aqueous fluid.
  • in another embodiment of the invention is a method of purifying solids permeable to aqueous fluid, said solids containing charged components, comprising the steps of
  • sorbed material is recovered together with the aqueous fluid having a reduced content of charged components.
  • One special embodiment of the invention is removing dissolved calcium in process waters in papermaking industry and thereby reducing the hardness of water.
  • the oxidized ligning containing material is recycled in a pulping process by returning part of the oxidized material to TMP-phase to be used as a sorbent for especially calcium ions.
  • said charged compounds are metal ions with any positive charge such as M1+, M2+, M3+ or M4+.
  • examples of such ions without limitation are, Pb, Cr, Cd, Ca, Mg, Mn, Zn, Co, Ni, Cu,' La.
  • the metals are heavy metals or Ca. Especially the heavy metals are hazard for the environment and typically the material to be purified is large. This invention provides safe and economic means for purifying large amounts of contaminated material.
  • the compounds so be sorbed are positively charged metal oxides such as vanadium oxide or organic molecules such as amines, amides or other ammonium derivates not excluding the ammonium ion.
  • Nitrogen containing compounds must be removed from waste streams in order to prevent eutrophication of nature waters.
  • the oxidized ligning containing material is used in a process of removing charged compounds or components, especially positively charged components such as ions from soil or other solids permeable to aqueous fluids.
  • Contaminated soil is contacted with an aqueous suspension of charged lignin- containing material for sorption of the charged compounds.
  • the sorbent materialused has a content of the carboxylic groups of at least 500 ⁇ /g dry weight and at least 750 ⁇ eq/g, preferably at least 1 meq/g, suitably at least 1.5 meq/g, for example 2 meq/g.
  • Lignin-containing material and sorbed components may be removed from the process with the aqueous fluid fraction or recovered by suitable separation methods such as flocculation, sedimentation, filtration, centrifugation or flotation.
  • Lignin-containing material can be used in combination with other sorption materials or other functional materials.
  • lignin-containing material or a fraction thereof is linked to a carrier, a membrane, or any other support material. This may be useful, e.g., in the creation of ion exchange materials, resins, functionalized beads, or adsorption columns.
  • the carboxyl charged oxidized lignin is combined with a support material to be used for ion exchange.
  • Charged lignin-containing material can be confined between two membranes or bound to a carrier material by e.g. grafting.
  • the lignin recovered after sorbent use can be burned for energy or used as a land filling material or as component of cement or concrete.
  • said lignin is regenerated before further use or in order to recover sorbed ionic compounds. This is needed when hazardous components such as heavy metals are sorbed. Regeneration also allows recovery of sorbed ionic compounds.
  • lignin precipitate was collected by centrifugation for 15 minutes at 4000 rpm, washed with water at pH 2.5 and centrifuged again. Thereafter lignin precipitate was freeze-dried. Two parallel samples were prepared and designated as BS311008 and BS 101108. In recovering the lignin fraction dissolved material mainly originated from hemi-celluloses mostly remains in the supernatant.
  • Spruce (Norway spruce, Picea abies) saw dust obtained from Hankasalmi saw mill was treated as described in WO2009/034325 except for shorter reaction time (5 hours, 120 °C, 10 bar initial 0 2 , and catalyst components: 300ppm o-phenanthroline monohydrate + 200 ppm CuS0 4 *5H 2 0).
  • a parallel oxidation treatment was also conducted without the presence of catalyst (5 hours, 120 °C, 10 bar initial 0 2 , no catalyst).
  • the filtrates were treated as described above.
  • the samples were designated as BS200209 (treatment conducted with Cu catalyst, CatOx) and BS230209 (treatment conducted without Cu catalyst, AlkOx).
  • the precipitated lignins were phosphitylated with 2-chloro-4,4,5,5-tetramethyl- 1,3,2- dioxaphospholane and analysed according to Granata et al. By the 31 P NMR analysis the different types of hydroxyl groups can be quantified separately. The analyses showed that the lignin precipitate BS311008 contains clearly more phenols and less carboxylic acid groups when compared to the precipitates BS200209 and BS230209 revealing that lignin in TMP reject pulp might be less reactive in the oxidizing treatment than lignin in saw dust.
  • the precipitate BS230209 (treatment conducted without Cu catalyst) contains slightly more aliphatic and phenolic hydroxyls and slightly less carboxylic acids, when compared to the precipitate BS200209 (treatment conducted with Cu catalyst).
  • Carboxylic group contents of lignin precipitates obtained when applying the oxidation treatment described in WO2009/034325 with or without the catalyst to spruce saw dust have been measured to be higher by Tamminen et al. (2.37 - 2.35 mmol/g) than presented in Table 3. above.
  • the carboxylic group content may also remain under 1 mmol/g, which is the case in TMP -reject pulp i.e. BS311008 (Table 3).
  • the processing history of the lignocellulosic raw material most likely effects the reactivity and the dissolution of lignin in the oxidation treatment.
  • Lignin-containing material obtained applying the oxidation treatment described in WO2009/034325 (with or without the catalyst) to raw material not pre-processed with high temperatures (> 130 °C) contains carboxylic acid groups in equal or in higher amount when comparing e.g. to that of lignosulphonates (a by-product of pulp and paper processes).
  • Table 4 shows the functional group content of purified sodium lignosulphate (SL) and fractions obtained from SL (Yang et al). The measurements of the functional groups were not conducted by 31 P NMR analysis. Therefore, the results shown in Table 3 and 4 are not absolute comparable. Table 4. Functional group content of purified sodium lignosulphate (SL) and fractions obtained from SL (Yang et al.).
  • the formation of acidic products in the oxidizing treatments was detected by pH measurements before and after the treatment, by conductometric titration of the filtrate and the lignin precipitate (latter dissolved in 1 M NaOH) and also by capillary electrophoresis (CE) analysis.
  • the total charge i.e. the sum of all acids was obtained and by the CE analysis small molecular weight acids (e.g such as formic, acetic, glycolic, and oxalic acids) formed both from lignin and hemicelluloses.
  • small molecular weight acids e.g such as formic, acetic, glycolic, and oxalic acids
  • the total charge of the sample was calculated by using the time difference between the equivalent points of acid and base titration curve.
  • This VTT method is a modification of the method described by Zakis.
  • CE analysis which is similar to that presented by Adler et al., alkaline background electrolyte and indirect UV detection were employed for analyzing aliphatic acids.
  • the content of lignin in the filtrate was calculated based on the UV absorbance at 280 nm using absorptivity 20 1/g cm (Tamminen & Hortling). Table 5. H and lignin content of the filtrate. In all treatments the initial pH after raw material and Na 2 C0 3 solution was above 11.
  • the chelate experiments showing the sorption ability of the lignin-containing material were conducted both with the filtrate samples and dry solids lignin precipitates. pH of the filtrate samples were adjusted to a level of 4.1 with 12 M HC1 and the dry solids lignin samples were dissolved 0.1 M NaOH before contacting with 100 ppm Ca 2+ solution. Lignin samples BS311008 and BS101108 to 200 mL, and BS200209 and BS230209 to small amount (ca. 4 mL) of 0.1 M NaOH. pH of the Ca 2+ solution was adjusted in a range of 5-6 with 0.1 M NaOH.
  • the samples were analyzed for their ability to chelate Ca 2+ -ions by measuring changes in free calcium concentration of the standard solution as a function of added lignin-containing sample-solutions prepared as described above.
  • Na 2 EDTA solution prepared from standard solution (9992 Titrisol , 0.1M, obtained from Merck) was used as a reference.
  • Calcium selective electrode was used to detect the changes in the Ca 2+ solution. The electrode is not for detecting the absolute values, but follows the changes satisfactorily. In addition, also pH was measured. At the beginning of the test the calcium content was 100 ppm. Calculated value for calcium binding by 0.372g EDTA was 40 ppm.

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Abstract

La présente invention concerne, d'une part des substances contenant de la lignine oxydée et certains de leurs dérivés, et d'autre part, leurs utilisations. L'invention concerne en particulier des substances contenant de la lignine oxydée capable d'éliminer par sorption, dans des fluides aqueux tels que les effluents industriels, des composants positivement chargés tels que les ions métalliques. L'invention concerne également un procédé permettant de purifier un fluide aqueux contenant des composants chargés, et un procédé permettant purifier des solides perméables au fluide aqueux et contenant des composants chargés.
PCT/FI2010/050932 2009-11-18 2010-11-18 Substance contenant de la lignine oxydée, utilisation de cette substance, et procédé de purification de fluides contaminés WO2011061399A1 (fr)

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CN103709772A (zh) * 2013-12-16 2014-04-09 华南理工大学 无机/木质素系聚合物复合纳米颗粒及其制备方法与应用
US20160074311A1 (en) * 2014-09-15 2016-03-17 Procter & Gamble International Operations Sa Consumer Goods Product Comprising Chitin, Lignin and a Polymer or Co-Polymer
EP2914773A4 (fr) * 2012-10-30 2016-06-15 Cyclewood Solutions Inc Injection d'un réactif chimique dans un flux de traitement contenant de la lignine
EP3059487A1 (fr) * 2015-02-19 2016-08-24 Melika International Business Handelsbolag Système et procédé de nettoyage d'huile
WO2017077198A1 (fr) * 2015-11-06 2017-05-11 Teknologian Tutkimuskeskus Vtt Oy Lignine oxydée en milieu alcalin par l'o2 utilisée comme dispersant
EP3266748A1 (fr) * 2016-07-06 2018-01-10 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
CN111346602A (zh) * 2020-03-20 2020-06-30 齐鲁工业大学 木质素磺酸钙衍生炭在去除废水中磷的应用
WO2020157386A1 (fr) * 2019-02-01 2020-08-06 Andritz Oy Procédé de production de lignine oxydée dans une unité de production de pâte kraft
CN112169753A (zh) * 2020-09-21 2021-01-05 张家港市杨舍丝印工艺厂 一种重金属吸附剂及其制备工艺
CN113842897A (zh) * 2021-10-23 2021-12-28 河南农业大学 一种吸附有机染料的环糊精聚合物制备方法
CN114295902A (zh) * 2021-12-30 2022-04-08 陕西科技大学 一种测定木质素纤维表面电荷密度的方法

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EP2914773A4 (fr) * 2012-10-30 2016-06-15 Cyclewood Solutions Inc Injection d'un réactif chimique dans un flux de traitement contenant de la lignine
CN103709772A (zh) * 2013-12-16 2014-04-09 华南理工大学 无机/木质素系聚合物复合纳米颗粒及其制备方法与应用
US20160074311A1 (en) * 2014-09-15 2016-03-17 Procter & Gamble International Operations Sa Consumer Goods Product Comprising Chitin, Lignin and a Polymer or Co-Polymer
EP3059487A1 (fr) * 2015-02-19 2016-08-24 Melika International Business Handelsbolag Système et procédé de nettoyage d'huile
WO2017077198A1 (fr) * 2015-11-06 2017-05-11 Teknologian Tutkimuskeskus Vtt Oy Lignine oxydée en milieu alcalin par l'o2 utilisée comme dispersant
CN108350177A (zh) * 2015-11-06 2018-07-31 芬兰国家技术研究中心股份公司 碱-o2氧化的木质素作为分散剂
EP3266748A1 (fr) * 2016-07-06 2018-01-10 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
WO2018007150A1 (fr) * 2016-07-06 2018-01-11 Clariant International Ltd Matériaux d'adsorption à base de lignine à faible coût pour le traitement de l'eau
US12054886B2 (en) 2019-02-01 2024-08-06 Andritz Oy Method for producing oxidized lignin in kraft pulp mill
WO2020157386A1 (fr) * 2019-02-01 2020-08-06 Andritz Oy Procédé de production de lignine oxydée dans une unité de production de pâte kraft
CN111346602A (zh) * 2020-03-20 2020-06-30 齐鲁工业大学 木质素磺酸钙衍生炭在去除废水中磷的应用
CN112169753B (zh) * 2020-09-21 2023-08-29 北京伟创力科技股份有限公司 一种重金属吸附剂及其制备工艺
CN112169753A (zh) * 2020-09-21 2021-01-05 张家港市杨舍丝印工艺厂 一种重金属吸附剂及其制备工艺
CN113842897A (zh) * 2021-10-23 2021-12-28 河南农业大学 一种吸附有机染料的环糊精聚合物制备方法
CN113842897B (zh) * 2021-10-23 2024-01-09 河南农业大学 一种吸附有机染料的环糊精聚合物制备方法
CN114295902A (zh) * 2021-12-30 2022-04-08 陕西科技大学 一种测定木质素纤维表面电荷密度的方法
CN114295902B (zh) * 2021-12-30 2024-03-08 陕西科技大学 一种测定木质素纤维表面电荷密度的方法

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