EP3814401A1 - Verfahren zur herstellung von ligninpartikeln - Google Patents
Verfahren zur herstellung von ligninpartikelnInfo
- Publication number
- EP3814401A1 EP3814401A1 EP19739851.4A EP19739851A EP3814401A1 EP 3814401 A1 EP3814401 A1 EP 3814401A1 EP 19739851 A EP19739851 A EP 19739851A EP 3814401 A1 EP3814401 A1 EP 3814401A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lignin
- precipitant
- particle
- containing solution
- particles
- 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.)
- Pending
Links
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
Definitions
- the present invention relates to a method for producing lignin particles by adding a precipitant to a particle-free lignin-containing solution.
- Lignins are solid biopolymers consisting of phenolic macromolecules that are embedded in the plant cell wall. In plants, lignins are primarily responsible for the strength of the plant tissue. In the production of cellulose or paper from plant material, the solid cell wall component lignin is separated from the cellulose by various processes (e.g. sulfite process, force digestion, organosolv process).
- Lignin is a highly irregularly branched polyphenolic polyether that consists of the primary monolignols, p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol exists, which are linked via aromatic and aliphatic ether bonds.
- softwood lignins are almost exclusively made up of coniferyl alcohol, hardwood lignins made of coniferyl and sinapyl alcohol and grass lignins from all three types.
- the high complexity and inhomogeneity of the lignin structure is in many cases even further increased by the pretreatment technologies currently used and leads to additional challenges for the further processing and recycling of the lignin.
- the lignin is extracted from the biomass in a relatively pure, low-molecular form with the Organosolv process used in the present case.
- This lignin shows a minimum of carbohydrate and mineral contaminants and facilitates applications of the lignin of higher value than the heat and energy generation.
- Nanostructured materials especially in the range of 1-100 nm, offer unique properties due to their increased specific surface, whereby their essential chemical and physical interactions are determined by the surface properties. Consequently, a nanostructured material can have significantly different properties than a larger dimensioned material of the same composition. Therefore, the production of lignin nanoparticles and other nanostructures has aroused interest among researchers in recent years.
- Lignin nanoparticles and microparticles find diverse potential applications, ranging from improved mechanical properties of polymer nanocomposites, bactericidal and antioxidative properties and impregnations, to drug carriers for hydrophobic and hydrophilic substances.
- carbonization of the lignin nanostructures can lead to high-quality applications such as use in supercapacitors for energy storage.
- US 2014/0275501 describes the production of lignin which has a lower degree of degradation than conventionally isolated lignin.
- Lignin is extracted from a biomass comprising lignin using a fluid comprising subcritical or supercritical water.
- the extractant can comprise, for example, methanol, ethanol or propanol, such a mixture comprising at least 80% by volume of the organic solvent.
- lignin can be precipitated from an extraction solution containing lignin by lowering the pH to about 2.
- WO 2016/197233 relates to an organosolv process with the aid of which high-purity lignin can be produced comprising at least 97% lignin.
- a lignin-containing starting material is first treated with a solvent mixture comprising ethanol and water in order to remove compounds from the starting material which dissolve in the solvent mixture.
- the lignin-containing material is then treated with a Lewis acid, which is also in a solvent mixture comprising, for example, ethanol and water.
- lignin is precipitated from the lignin-containing solution by lowering the pH.
- NZ 538446 relates to processes for the treatment of lignin-containing materials, such as e.g. Wood, for example to incorporate active substances into it.
- lignin-containing materials such as e.g. Wood
- active substances such as e.g. Wood
- a method for producing lignin particles is not disclosed.
- WO 2010/058185 describes a method for treating biomass, in the course of which the biomass is separated into lignin and other components using ultrasound and an aqueous solvent system.
- lignin is obtained by evaporation from a water-immiscible solvent.
- WO 2012/126099 also describes an organosolv process by means of which aromatic compounds, ie lignin, can be isolated from a biomass and precipitated by evaporation or lowering of the pH.
- WO 2013/182751 discloses methods for fractionating lignin, in which lignin is first dissolved with an organic solvent and water. The mixture is then ultrafiltered, so that lignin fractions can be produced that have a certain molecular weight. The lignin can then be precipitated.
- WO 2010/026244 relates inter alia to various organosolv processes with which cellulose can be produced, which among other things is enriched with lignin.
- Lignins and especially nanolignin are used in a variety of industrial applications.
- the nanolignin obtained can be further processed in a variety of ways, for example by chemical (e.g. medically or enzymatically active) ligands can be fixed to the nanolignin or the nanolignin can be made UV-protective by ultrasound treatment.
- Nanolignin-based plastics are characterized by high mechanical stability and hydrophobic properties (dirt-repellent). This makes them suitable for many areas of application, including e.g. for use in the automotive industry.
- nanolignin can be used in different types of fillings, as reinforcing fibers and the like. Find application.
- the relevant literature shows, for example, that a controlled polymerization of nanolignin particles with styrene or methyl methacrylate results in a tenfold increase in material resistance compared to a lignin / polymer mixture.
- Nanolignin applied to textile surfaces provides active protection against UV radiation. This can lead to an application in the production of functional textiles.
- the moisture-repellent and antibacterial properties of nanolignin open up areas of application in the packaging industry (production of special Packaging films), especially in the field of food packaging.
- Lignin nanoparticles can be permeated with silver ions and coated with a cationic polyelectrolyte layer, so that there is a naturally degradable and "green” alternative to silver nanoparticles.
- Nanolignin suitable, among other things. for use in biofilms for implants.
- Nanolignin can also be used in the pharmaceutical industry e.g. be used in the field of drug delivery.
- Lignin particles are currently mainly produced by dissolving lignin that has already been isolated and precipitated (mostly using lignin sulfonates or lignosulfonate sources, e.g. black liquor or alkali metal lignin).
- the lignin precipitated for the first time has no particle or nanoparticle structure.
- These structures can be created by first dissolving lignin that has already been precipitated and then reprecipitating it or grinding it on the other hand (see CN 103145999).
- Lignin particles or nanolignin can also be produced from black liquor, a lignin-rich by-product or waste product in the manufacture of paper or cellulose, using CCb high-pressure extraction (CN 102002165).
- CN 104497322 describes a method in which a lignin solution treated with ultrasound is added dropwise to deionized water and then nanolignin is separated off by means of a centrifuge.
- the present invention has as its object to provide processes for the production of lignin particles from solutions containing lignin, with which lignin nanoparticles can be produced which are reproducible and as homogeneous as possible in terms of their size distribution, the processes being cost-effective and should be time-efficient and easily transferable to industrial scale.
- the particles obtained should be nanoparticles and their average size should be less than 400 nm, preferably less than 300 nm, more preferably less than 200 nm or even more preferably less than 100 nm.
- the present invention relates to a process for the production of lignin particles in the context of a continuous process in which a particle-free lignin-containing solution and a precipitant are brought together in a mixer and then passed out of the mixer again, with a mixing quality of the lignin-containing solution with the precipitant from at least 90% and a precipitation of lignin particles is achieved, whereby a suspension of lignin particles is formed, which is characterized in that the residence time in the mixer does not exceed a period of 5 seconds.
- the present invention relates to a process for the production of lignin particles in the context of a continuous process, in which a particle-free lignin-containing solution and a precipitant are brought together in a mixing device and then passed out again from the mixing device, the quality of the lignin-containing solution being mixed with the precipitant from at least 90% and a precipitation of lignin particles is achieved, whereby a suspension of lignin particles is produced, the mixing device comprising at least one mixer and the line leading therefrom with a diameter of 10 mm or smaller, which is characterized in that the residence time in the mixing device does not exceed a period of 30 seconds.
- the method according to the invention can be carried out with water alone as the precipitant, which enables extremely simple, fast, environmentally friendly and inexpensive large-scale production of such lignin particles.
- a comparable yield of lignin particles can be achieved if pure water as a precipitant compared to a mixture of water and sulfuric acid with a pH of 5 as a precipitant, as described in Beisl et al. (Molecules 23 (2016), 633-646) is used.
- the present invention is characterized in that in a continuous process the lignin precipitation step is carried out in a mixing step which is shortened compared to the prior art.
- the method can therefore be defined in that the dwell time in a mixer or in the entire mixing device is kept very short (that is, less than 5 seconds in the mixer or less than 30 seconds in the entire mixing device).
- a “mixing device” is understood to mean a unit in the continuous process for producing the lignin particles, in which the particle-free lignin-containing solution is contacted and mixed with the precipitant and the lignin particles are precipitated.
- this consists at least of a mixer , in which the particle-free lignin-containing solution is mixed with the precipitant in such a way that the two components are mixed as extensively as possible and within a very short time.
- the precipitation process according to the invention is generally essentially completed in the short residence time in the mixer , ie that the particle size of the lignin particles is already essentially complete is defined.
- size changes are then generally made possible or achieved only by means of targeted or random procedural measures, for example by aggregation.
- the “precipitation process” is in any case already completed in the mixer when there is a mixing quality (mixing) of the particle-free lignin-containing solution more than 90 or 95% of the precipitant is used. In exceptional cases, however, further mixing (and thus possibly precipitation processes) can also occur in the discharges from the mixer, for example due to wall friction, if the mixing of the particle-free lignin-containing solution with the precipitant in the mixer was insufficient.
- the mixing process of the present invention in which the precipitation of the lignin particles is achieved, can also be carried out in a mixing device which, in addition to the actual mixer, also comprises (thin) lines in which, due to wall friction and a small diameter, any from the mixer still incompletely mixed precipitant / lignin solution can experience further mixing and precipitation.
- a mixing device which, in addition to the actual mixer, also comprises (thin) lines in which, due to wall friction and a small diameter, any from the mixer still incompletely mixed precipitant / lignin solution can experience further mixing and precipitation.
- lines with a diameter of 10 mm or smaller, in particular 5 mm or smaller are suitable for this.
- a “particle-free lignin-containing solution” is understood to mean any solution in which lignin is dissolved and which does not contain any particles which interfere with the precipitation of lignin particles and their intended use.
- particle-free lignin-containing solution Depending on the type of preparation of the particle-free lignin-containing solution and the lignin-containing starting material In order to produce “particle-free” lignin-containing solutions, physical or chemical cleaning steps, with which such particles may be removed, may have to be provided.
- the “particle-free lignin-containing solution” is therefore either to be understood as a solution saturated with lignin or a diluted form thereof with regard to the lignin concentration.
- the lignin concentration is therefore at given conditions below the solubility limit.
- the particle-free lignin-containing solution is preferably specified in the context of the method according to the invention under conditions and using solvents which allow the highest possible lignin concentration.
- the "precipitant” is then used to bring about a state in which the solubility limit in the particle-free lignin-containing solution is exceeded.
- this can be achieved both by adding liquid, gaseous and solid precipitants to the mixer; however, the addition of Liquid precipitants can be supplied relatively easily in the continuous process stream of the particle-free lignin-containing solution (for example by separate feeding into the mixer, through a T-piece immediately before the mixer or by introducing the precipitant into the solution stream also immediately before the mixer).
- the short contact time or the short mixing time in the mixer of 5 seconds or less is available according to the invention a little more complex in terms of ear technology, especially if ordinary water is to be used as a precipitant.
- the “mixing quality” is defined by the variance of the concentrations in a control volume.
- the control volume is an infinitesimally small length of the flow cross-section.
- the coefficient of variation is the quotient of the standard deviation of the chemical composition of samples from the mixing room and the arithmetic mean of the samples.
- the mixing space is the cross-section of the mixer tube with an infinitesimally small length. The value can thus be interpreted as a relative error of the target composition over the mixer cross section.
- a mixing quality of 90% is preferably achieved immediately after the mixing device. Even more preferably, a mixing quality of 90% is achieved immediately after the mixer.
- the “mixing quality” is the variance of the concentrations of solvent of the lignin-containing solution and precipitant.
- the mixing quality is preferably determined by spatially resolved measurement of the concentrations.
- the measurement of the mixing quality is preferably carried out during the operation of the mixing device by means of non-invasive methods based on laser technology, and here preferably by means of Raman spectroscopy, preferably in combination with spatially resolved laser Doppler anemometry.
- the local composition and flow velocity are measured on a flow-through line cross section using laser technology.
- the exact procedure for the measurement is the AT 520.087 Bl or the publication Haddadi B., et al. Chemical Engineering Journal 334, 2018, 123-133.
- Micro Particle Image Velocimetry can be used as a non-invasive method.
- the Micro Particle Image Velocimetry (mR ⁇ n) and in particular the 3D pPIV is a standard method for determining the flow processes on a microscale. However, it can also be used to determine the mixing quality when mixing two liquids if one of the two liquids is admixed with non-Brownian particles. The exact procedure for the measurement can be found in the following sources: Raffel, Markus, et al. Particle image velocimetry: a practical guide. Springer, 2018; Hoffmann, Marko, et al. Chemical engineering Science 61.9 (2006): 2968-2976.
- the mixing quality can also be determined theoretically using numerical flow simulation CFD.
- fluid mechanical problems are preferably modeled using Navier-Stokes equations and solved numerically using the finite volume method.
- the quality of the mixture of two fluids can be predicted with high reliability in a purely theoretical way in the entire flow space under consideration.
- Commercial software packages requiring a license such as ANSYS Fluent, ANSYS CFX or Star-CCM from CD-adapco, or packages from the open source area such as OpenFOAM can be used for this.
- the correct procedure can be found in the available literature: Bothe, Dieter, et al. Chemistry Engineer Technology 79.7 (2007): 1001-1014 .; Ehrentraut, Michael. Numerical investigations on the quality of mixing when stirring viscoplastic fluids: Flow simulation for the analysis of stirred, rheologically complex fluids. Springer publishing house, 2016.
- Another alternative method for determining the mixing quality is invasive isokinetic sampling from the flow and subsequent ex-situ analysis of the composition of the sample taken using high-performance liquid chromatography (HPLC).
- HPLC high-performance liquid chromatography
- isokinetic sampling is of crucial importance.
- the fluid flowing into the sample collector must have the same flow rate as the surrounding fluid in order to adulterate the composition of the sample taken prevent.
- the procedure for isokinetic sampling is very well defined for particle-laden gas flows and, in this form, also applies analogously to liquid flows.
- the method according to the invention is characterized above all by the provision of a short mixing or contact time between the particle-free lignin-containing solution and the precipitant. This should enable essentially complete precipitation within this short time, as a result of which the lignin particles desired according to the invention are formed. According to the invention, the residence time in the mixer should therefore not exceed a period of 5 seconds.
- the residence time in the mixer is not more than 4 seconds, preferably not more than 3 seconds, even more preferably not more than 2 seconds, in particular not more than 1 second.
- Such short mixing times have nevertheless proven to be sufficient to obtain the desired lignin particles in the desired quality and size.
- the residence time in the mixer is preferably at least 0.1 seconds, preferably at least 0.3 seconds, even more preferably at least 0.5 seconds, in particular at least 0.6 seconds, most preferably at least 0.7 seconds.
- the residence time in the mixer is between 0.1 and 5 seconds, preferably between 0.3 and 4 seconds, even more preferably between 0.5 and 3 seconds, in particular between 0.6 and 2 seconds, most preferably between 0.7 and 1 seconds.
- the dwell time in the mixing device in particularly preferred embodiments is not more than 25 seconds, preferably not more than 20 seconds, in particular not more than 15 seconds.
- the residence time in the mixing device is preferably at least 0.5 seconds, preferably at least 1.5 seconds, even more preferably at least 3 seconds, in particular at least 4 seconds, most preferably at least 5 seconds.
- the residence time in the mixing device is between 0.5 and 30 seconds, preferably between 1.5 and 25 seconds, even more preferably between 3 and 20 seconds, in particular between 4 and 18 seconds, most preferably between 5 and 15 seconds.
- the mixer according to the invention is preferably selected from a static mixer, a dynamic mixer or combinations thereof.
- a static mixer contains no moving parts and is therefore also referred to as a "passive mixer".
- Dynamic mixers according to the present invention include mixers with moving mechanical parts as well as all active mixers. In active mixers, the energy required for the relative displacement is required from particles of the raw materials, not related to the raw materials themselves (eg ultrasonic waves, vibrations due to rising bubbles or pulsating inflow).
- Passive" mixers include all mixers in which the energy required is withdrawn from the incoming raw materials.
- the particle-free lignin-containing solution preferably comprises at least one organic solvent and water.
- the particle-free lignin-containing solution can be made available in all possible ways. In principle, however, are preferred lignin-containing solutions from established industrial processes are used as starting material in the process according to the invention. Accordingly, the particle-free lignin-containing solution is preferably by a Kraft Lignin (KL) process, a Soda Lignin process, a Lignosulfonate (LS) process, an Organosolv Lignin (OS) process, a steam explosion - Lignin process, a hydrothermal process, an ammonia explosion process, a supercritical CCL process, an acid process, an ionic liquid process, a biological process or an enzymatic hydrolysis lignin (EHL) Procedure received.
- KL Kraft Lignin
- Soda Lignin process a Soda Lignin process
- LS Lignosulfonate
- OS Organosolv Lignin
- EHL enzymatic hydrolysis lignin
- the lignin preparations resulting from these processes can be converted into a particle-free lignin-containing solution which are fed to the method according to the invention by additional suitable steps.
- EHL lignin can only be obtained after pretreatment with one of the other processes described and subsequent enzymatic hydrolysis. The lignin then remains as a solid and must first be dissolved in a solvent in order to obtain a solution containing lignin.
- the precipitant is water or a dilute acid, preferably sulfuric acid, phosphoric acid, nitric acid or an organic acid, in particular formic acid, acetic acid, propionic acid or butyric acid, or C0 2 , water being particularly preferred as the precipitant.
- the precipitant is added in such a way that lignin particles form from the lignin-containing solution.
- the solubility limit must be exceeded by adding the precipitant.
- the precipitant is preferably a solution and the volume of the precipitant is at least 0.5 times, preferably at least 2 times, in particular at least 5 times, the volume of the lignin-containing solution or the volume of the precipitant is 1 times up to 20 times, preferably 1.5 times to 10 times, in particular 2 times to 10 times, the volume of the lignin-containing solution.
- a liquid precipitant is therefore preferably added such that the concentration of the solvent in the lignin-containing solution in the range of 1 to 10,000 wt% / s, preferably 10 to 5,000 wt% / s, preferably 10 to 1,000 wt% / s, preferably 10 to 100 wt% / s, in particular 50 to 90 wt% / s, in the mixed / The precipitation process is reduced.
- the pH of the precipitant is in the range from 2 to 12, preferably from 3 to 11, in particular from 4 to 8, or the pH of the suspension of lignin particles in the range from 2 to 12, preferably from 3 to 11, in particular from 4 to 8.
- a substantially complete mixing is preferably achieved in the mixing device or in the mixer. Accordingly, according to preferred embodiments, a mixing quality of the lignin-containing solution with the precipitant of at least 95%, preferably at least 98%, in particular at least 99%, is achieved.
- the particle-free lignin-containing solution contains an organic solvent, preferably an alcohol, a ketone or THF, ethanol being particularly preferred, in particular in a mixture with water.
- an organic solvent preferably an alcohol, a ketone or THF
- ethanol being particularly preferred, in particular in a mixture with water.
- the water / ethanol system for dissolving lignin is well described and known in the present field, especially with regard to the optimal solution conditions and also with regard to the quantitative precipitation conditions.
- some of these parameters are not as critical in the method according to the invention as described in the prior art.
- the dependence of the yield on the pH value is surprisingly not so critical in the context of the present invention; in fact, according to the invention, they proved the yields, for example at pH 5 and pH 7, to be quite comparable.
- the particle-free lignin-containing solution preferably contains an organic solvent, preferably a Ci to Cs alcohol, especially selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, ethane-1,2-diol, propane-1,2 -diol, propane-1,2,3-triol, butane-1,2,3,4-tetraol and pentane-1,2,3,4,5-pentol; or a ketone selected from acetone and 2-butanone.
- the particle-free lignin-containing solution preferably contains an organic solvent in an amount of 10 to 90% by weight, preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, even more preferably 40 to 60% by weight, even more preferably 50 to 65 % By weight.
- organic solvents are suitable in principle as lignin-dissolving solvents (only these are of course to be regarded as “organic solvents” according to the present invention according to the invention), but also in what amount they are to be used in principle (for example also in a mixture with water). and at what amounts or under what conditions the solubility of lignin is particularly high.
- the method according to the invention can in principle be carried out at all temperatures at which the particle-free lignin-containing solution is in liquid form.
- process temperatures are preferably used in accordance with the invention, which allow the process to be operated efficiently and possibly in an energy-saving manner.
- the precipitation according to the invention is therefore carried out at from 0 to 100 ° C., preferably from 5 to 80 ° C., more preferably from 10 to 60 ° C., even more preferably from 15 to 50 ° C., even more preferably from 20 to 30 ° C.
- the precipitation process according to the invention can be carried out at room temperature or at ambient temperature.
- the particle-free lignin-containing solution is a saturated lignin solution or a dilute form thereof.
- the absolute concentration of lignin in a saturated solution is of course different.
- Particle-free lignin-containing solutions are preferably used according to the invention, the lignin in an amount of 0.1 to 50 g lignin / L, preferably 0.5 to 40 g / L, even more preferably 1 to 30 g / L, even more preferred from 2 to 20 g / L.
- the suspension with the lignin particles obtained is passed on from the mixer or the mixing device and subjected to the further production process.
- lignin particles or the suspension of lignin particles are therefore preferably introduced into a suspension container after the mixer or after the mixing device.
- no fundamental changes are made to the lignin particles at this stage of the process, in particular no further significant precipitation processes or processes that significantly shift the particle size downwards. If desired, targeted aggregation processes can be initiated.
- the precipitation process according to the invention can be based on particle-free lignin-containing solutions of various origins.
- lignin is obtained by extracting raw materials containing lignin.
- the particle-free lignin-containing solution is preferably obtained by extraction of lignin-containing starting material, selected from material of perennial plants, preferably wood, wood waste or shrub cuttings, or material from annual plants, preferably straw, or biogenic waste.
- the lignin-containing starting material can have an average size of from 0.5 to 50 mm, preferably from 0.5 to 40 mm, even more preferably from 0.5 to 30 mm, even more preferably from 1 to 25 mm, even more preferably from 1 to 20 mm, more preferably 5 to 10 mm, are subjected to the extraction process.
- the extraction of lignin-containing starting material is preferably carried out at a temperature of 100 to 230 ° C, preferably 120 to 230 ° C, more preferably 140 to 210 ° C, even more preferably 150 to 200 ° C, even more preferably from 160 to 200 ° C, more preferably from 170 to 200 ° C, even more preferably from 170 to 195 ° C, even more preferably from 175 to 190 ° C.
- the extraction of lignin-containing starting material can be carried out, for example, at a pressure of 1 to 100 bar, preferably 1.1 to 90 bar, even more preferably 1.2 to 80 bar, even more preferably 1.3 to 70 bar, even more preferably 1. 4 to 60 bar.
- the particle-free lignin-containing solution is obtained by extraction of lignin-containing starting material and subsequent removal of solid particles still present in the extraction mixture.
- the particles obtainable according to the invention are of high quality, above all with regard to their nanoparticle properties, size distribution and homogeneity. Despite the short precipitation time according to the invention, the particles obtained have a comparatively very small diameter.
- the lignin particles obtainable according to the invention have an average diameter in the suspension of less than 400 nm, preferably less than 250 nm, even more preferably less than 200 nm, even more preferably less than 150 nm, in particular less than 100 nm, on.
- At least 50% or more of the lignin particles obtainable according to the invention have, according to likewise preferred variants of the method according to the invention, a size in the suspension, measured as hydrodynamic diameter (HD), in particular measured with dynamic light scattering (DLS), of less than 400 nm, preferably less than 300 nm , even more preferably from below 250 nm, in particular from below 150 nm, even more preferably from below 100 nm.
- HD hydrodynamic diameter
- DLS dynamic light scattering
- At least 60% or more, preferably at least 70% or more, more preferably at least 80% or more, in particular at least 90% or more, of the lignin particles obtainable according to the invention have a size in the suspension, measured as a hydrodynamic diameter, according to likewise preferred variants of the method according to the invention (HD), in particular measured with dynamic light scattering (DLS), of less than 500 nm, preferably of less than 300 nm, even more preferably of below 250 nm, even more preferably from below 200 nm, in particular from below 100 nm.
- HD dynamic light scattering
- Figure 3 Distribution of the hydrodynamic diameter of and SEM images of lignin particles that were precipitated directly from Organosolv extract or from a solution of purified lignin.
- the parameters used were pH 7, precipitant / extract ratio of 5 and a flow rate of 112.5 ml / min in the static mixer.
- FIG. 4 (a) Boxplot diagram of the relative carbohydrate content found in the 34 individual experiments, (b) Boxplot diagram of the total carbohydrate content in the direct precipitation from organosolv extracts and in the purified lignin.
- lignin has improved properties over standard lignin available today and has gained interest in recent years.
- Lignin is the largest renewable Resource on earth with an aromatic skeleton, but is used for relatively low-value applications.
- the use of lignin on a micro to nano scale could, however, lead to valuable applications.
- Current manufacturing processes consume large amounts of cleaning and precipitation solvents.
- the method investigated in this work uses the direct precipitation of lignin nanoparticles from organosolv pretreatment extract in a static mixer and can drastically reduce the solvent consumption. pH value, ratio of precipitant to organosolv extract and flow rate in the mixer were investigated as precipitation parameters with regard to the resulting particle properties.
- Particles in the size range from 97.3 nm to 219.3 nm could be produced, and with certain precipitation parameters, the carbohydrate contamination reaches values as low as in cleaned lignin particles.
- the yields were 48.2 + 4.99% regardless of the precipitation parameters.
- the results presented can be used to optimize the precipitation parameters with regard to particle size, carbohydrate contamination or solvent consumption.
- the degree of lignin supersaturation, the hydrodynamic conditions prevailing during the process and the pH of the fluid surrounding the particles are important parameters that determine the final Affect particle size and behavior. These process conditions mentioned are examined by varying the precipitation parameters pH value, ratio of precipitant to OSE and the flow rate in the static mixer. The resulting particles were examined for particle size, stability, carbohydrate contamination and yield of the process. The best precipitation parameters were identified and a comparison was made with the precipitation of the previously cleaned and redissolved lignin.
- the wheat straw used was harvested in the state of Lower Austria in 2015 and stored under dry conditions until use.
- the particle size was comminuted in a granulator equipped with a 5 mm sieve before the pretreatment.
- the composition of the dry straw was 16.1% by weight of lignin and 63.1% by weight of carbohydrates, consisting of arabinose, glucose, mannose, xylose and galactose.
- Ultrapure water (18 MW / cm) and ethanol (Merck, Darmstadt, Germany, 96% by volume, undenatured) were used in the organosolv treatment, and sulfuric acid (Merck, 98%) was also used in the precipitation steps.
- the Organosolv pretreatment was carried out as previously described in Beisl et al. (Molecules 23 (2016), 633-646). Briefly, wheat straw was treated at a maximum temperature of 180 ° C for 1 h in 60% by weight aqueous ethanol. Residual particles were separated by centrifugation. The composition of the extract can be found in Table 1.
- the precipitation arrangement used is generally described in Beisl et al. (Molecules 23 (2016), 633-646). However, compared to Beisl et al. that in the mixing device (consisting of the T-connector, a The 20.4 cm long tube with an inner diameter of 3.7 mm, which contains the static mixing elements and the 1 m long rubber hose (diameter 4 mm), was chosen to be considerably shorter for the present invention. While in Beisl et al.
- the time in the static mixer was more than 36 s (volume: about 15 ml with a flow rate of about 24 ml / min) and the time in the static mixer itself was more than 5 s (volume: about 2.2 ml with a flow rate of about 24 ml / min), shorter mixing times are used in the process according to the present invention (30 s or less).
- the time in the mixing device in the present examples is in the range from about 23 s to 3 s and the time in the mixer in the present examples is in the range from about 5 s to 0.6 s.
- the arrangement consists of two syringe pumps, a static mixer and a stirred collecting vessel.
- the stirrer speed in the collecting vessel was set to 375 rpm.
- the acidified precipitants with a pH of 3 and 5 were adjusted with sulfuric acid and the pH 7 precipitant was pure water.
- the particles were separated from the suspension after precipitation in a ThermoWX-80 + ultracentrifuge (Thermo Scientific, Waltham, MA, USA) at 288,000 g for 60 min. The supernatant was decanted and the precipitated substance was freeze-dried.
- lignin was precipitated from the same extraction process and purified by repeated ultrasound treatment, centrifugation and replacement of the supernatant.
- purified lignin (“purified lignin”; PL) was freeze-dried and then dissolved in an ethanol / water mixture at the same ethanol concentrations compared to undiluted OSE. This artificial extract was used for comparison with the direct precipitation.
- the experimental design and the statistical evaluation of the results were carried out using the software Statgraphics Centurion XVII (Statpoint Technologies, Inc., USA).
- a face-centered (face-centered) central composite design comprising three central points with a full repetition (34 individual experiments) was used for the precipitation parameters flow rate in the static mixer, pH value of the precipitation agent and volume ratio of precipitation agent to OSE.
- the flow rates in the static mixer were set at 37.5 ml / min, 112.5 ml / min and 187.5 ml / min.
- the precipitant to extract volume ratio was adjusted to 2, 5 and 8, while the pH of the precipitant was 3, 5 and 7.
- the ethanol concentration-dependent turbidity of the particle suspension was determined using a Hach 2100Qis (Hach, CO, USA). To remain within the calibration range, the extract was diluted 1: 6 by volume with ethanol / water to maintain the undiluted ethanol concentration of the extract. Water or sulfuric acid / water mixtures were gradually added to a stirred vessel filled with the diluted extract and measured after each addition.
- the hydrodynamic diameter (HD) of the particles was measured using dynamic light scattering (DLS) (ZetaPALS, Brookhaven Instruments, Holtsville, NY, USA). The measurements were carried out in the particle suspension directly after precipitation - both undiluted and in a 1: 100 dilution with pure water. Undiluted measurements were corrected for their viscosity and the refractive index of the supernatant obtained after centrifugation. For long-term stability tests, the particles were stored at 8 ° C, but measured at 25 ° C.
- DLS dynamic light scattering
- the z-potential was examined with a ZetaPALS (Brookhaven Instruments, Holtsville, NY, USA). Dried particles were in water at an appropriate Concentration of 20 mg / L dispersed and aged for 24 h before measurement. Each measurement consisted of five runs, each with 30 sub-runs, and was carried out at 25 ° C.
- Freeze-dried particles were dispersed in hexane, spread on a sample holder and examined in a scanning electron microscope (SEM) (Fei, Quanta 200 FEGSEM). The samples were sputter coated with 4 nm Au / Pd (60 wt% / 40 wt%) before analysis.
- SEM scanning electron microscope
- the carbohydrate content was determined using the sample preparation in accordance with the laboratory analytical procedure (LAP) of the National Renewable Energy Laboratory (NREL): "Determination of Structural Carbohydrates and Lignin in Biomass" (Sluiter et al., Determination of Structural Carbohydrates and Lignin in Biomass; Denver , 2008), but the samples were not neutralized after hydrolysis.
- LAP laboratory analytical procedure
- NREL National Renewable Energy Laboratory
- the yield was determined on the basis of the difference in the dry matter content of the particle suspension directly after precipitation and the supernatant of the particle suspension after centrifugation.
- the solubility of lignin strongly depends on the ethanol concentration in ethanol / water solvent mixtures and the type of lignin (Buranov et al., Bioresour. Technol. 101 (2010), 7446-7455).
- the turbidity was measured as a function of the ethanol concentration (see FIG. 1). Pure water and water / sulfuric acid mixtures were gradually added to the OSE in a stirred flask at an initial ethanol concentration of 56.7% by weight.
- the Initial OSE diluted by a factor of 1: 6 by mass while maintaining the initial ethanol concentration.
- the undiluted lignin concentration of 7.35 g / kg was therefore reduced to 1.23 g / kg. This could lead to a slight shift in the turbidity maxima towards lower ethanol concentrations, since the solubility limit is reached at lower ethanol concentrations.
- the maxima of the turbidity curves are used to determine the minimum precipitant / OSE ratios required for the precipitation.
- the turbidity maxima are reached at 19.9% by weight, 18.1% by weight and 17.9% by weight for adding precipitants with a pH of 2, 5 and 7, respectively.
- the lowest precipitant / OSE ratio for the precipitation experiments was therefore set at 2, which led to a final ethanol concentration in the suspension of 17.6% by weight.
- the independent variables pH of the precipitant, flow rate in the static mixer and precipitant / OSE ratio were examined in relation to the resulting particle HD.
- the resulting particle suspensions were measured by dynamic light scattering (DLS) directly after precipitation in two variants: undiluted and in a 1: 100 dilution with water. After correcting the viscosity and the refractive index for the undiluted samples, the HDs for both dilution variants were compared with a paired t-test and showed significantly identical results for both conditions.
- the results shown in Figure 2 are based on the HDs obtained by diluted measurements.
- the resulting HDs range from 97.3 nm to 219.3 nm.
- the smallest HD is achieved in precipitation with a precipitant / OSE ratio of 6.29, pH 7 and a flow rate of 132.06 ml / min.
- the particles with the highest HD result from a precipitant / OSE ratio of 2, pH 4.93 and a flow rate of 187.5 ml / min.
- the HD of the particles shows a strong dependence on the flow rate with minima of between 107.25 ml / min and 138.0 ml / min depending on pH and ratio. This behavior could arise from changing flow conditions that affect the balance of primary nucleation and agglomeration by changing the supersaturation of lignin and the collision rate of the resulting particles.
- supersaturation is comparatively low and larger particles are formed.
- the supersaturation of the lignin increases, which leads to smaller particles.
- further increased supersaturation leads to higher collision and agglomeration rates (Lewis et al., Industrial Crystallization; Cambridge University Press: Cambridge, 2015; pp. 234-260).
- HDs decrease with increasing ratios due to higher supersaturation and coherently increasing nucleation rates.
- the HD of the particles decreases from 172.9 nm to 117.3 nm and 101.7 nm for ratios of 2, 5 and 8, respectively .
- the mechanical energy supply does not increase due to the constant flow rate.
- the particle collision rates therefore only depend on the particle concentrations. Consequently, higher precipitant / OSE ratios coherently lead to lower agglomeration (Lewis et al., Industrial Crystallization; Cambridge University Press: Cambridge, 2018; pp. 130-150).
- the pH shows the least influence of the examined variables on the HD.
- the HD increases from 104.0 nm to 131.2 nm by raising the pH of the precipitant from 3 to 7 at a constant precipitant / OSE ratio of 5 and a flow rate of 112.5 ml / min.
- the increased HD at low pH values could be explained by the z-potential of the particles, which decreases to pH values of 3 and reaches the isoelectric point at pH values of around 2.5.
- the OSE contains not only lignin, but also components such as carbohydrates, acetic acid and various breakdown products, which must be considered as contaminants during the precipitation process.
- lignin was purified from the OSE used and dissolved in an aqueous ethanol solution with an ethanol concentration of 56.7% by weight, equal to the undiluted OSE.
- the solubility of the PL reached its limit at a concentration of 6.65 g / kg, which is lower than the lignin concentration of 7.35 g / kg in the OSE. Therefore, the OSE was diluted to the same lignin concentration with a constant ethanol concentration.
- the precipitation parameters were set to pH 7, ratio 5 and a flow rate of 112.5 ml / min, which is the closest experimental point to the calculated parameters for the smallest particles.
- the HD distributions and SEM images of the precipitation directly from OSE and the dissolved PL are shown in FIG. 3.
- the PL precipitation results in an HD of 77.6212.74 nm, whereas the precipitation directly from the OSE leads to a higher HD of 102.717.75 nm.
- a comparable result was found by Richter et al. (Langmuir 2016, 32 (25), 6468-6477) with organosolv lignin, dissolved in acetone, and a precipitation which led to particles with a diameter of about 80 nm.
- the SEM images show only slight differences and separate particles in both cases. Based on the DLS results, however, the impurities can have a negative impact on particle size.
- the OSE also contains carbohydrates as a major source of contaminants during precipitation.
- the total carbohydrate content in the extract is 10.2% of the lignin content. Therefore, the resulting precipitated substance was analyzed for its carbohydrate content after centrifugation and freeze-drying.
- FIG. 4a The relative proportion of the carbohydrates is shown in Figure 4a. Glucose, with a relative proportion of 47.213.36%, is the predominant carbohydrate compound in the precipitated substance.
- FIG. 4b compares the carbohydrate concentrations found in the precipitated substance from the direct OSE experiments with the PL precipitates. The total carbohydrate content in the PL is 2.4110.25% by weight and appears to be covalently bound to the lignin. The lowest carbohydrate content found within all direct OSE precipitates was 2.39% by weight, which is in the concentration range of the PL. This shows that certain precipitation parameters allow a precipitation of almost pure lignin based on the carbohydrates dissolved in the OSE that remain on the particles.
- FIG. 4b compares the carbohydrate concentrations found in the precipitated substance from the direct OSE experiments with the PL precipitates. The total carbohydrate content in the PL is 2.4110.25% by weight and appears to be covalently bound to the lignin. The lowest carbohydrate content
- the carbohydrate concentrations for a ratio of 2 are between 2.35% by weight and 2.80% by weight for precipitations with pH 3 and a flow rate of 187.5 ml / min or pH 4.79 and a flow rate of 37 , 5 ml / min.
- a concentration minimum of 3.47% by weight and a maximum of 6.10% by weight can both be used at a flow rate of 187.5 ml / min and a pH of the precipitant of 3 and 7, respectively being found .
- the pH value shows an increasing influence on increasing precipitant / OSE ratios and flow rates.
- the carbohydrate concentration with otherwise constant precipitation parameters can be reduced by up to 43% by changing the pH of the precipitation agent. This maximum reduction is achieved with a precipitant / OSE ratio of 8 and a flow rate of 187.5 ml / min, and the Carbohydrate content can be reduced from 6.09% by weight to 3.47% by weight by changing the pH from 7 to 3.
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US11840776B2 (en) * | 2018-02-26 | 2023-12-12 | The Texas A&M University System | Lignin fractionation and fabrication for quality carbon fiber |
CN109456496A (zh) * | 2018-11-26 | 2019-03-12 | 广州楹鼎生物科技有限公司 | 一种木质素的纯化方法 |
WO2020248048A1 (en) | 2019-06-13 | 2020-12-17 | 2599218 Ontario Inc. | Apparatuses, methods, and systems for fabricating graphene membranes |
WO2021046199A2 (en) * | 2019-09-05 | 2021-03-11 | Ut-Battelle, Llc | Lignin dispersion composition and its use in stabilizing emulsions |
CN112646196A (zh) * | 2020-12-18 | 2021-04-13 | 安徽工业大学 | 一种利用酸沉降和透析从木质素提取液中制备纳米木质素的方法 |
EP4023813A1 (de) * | 2020-12-29 | 2022-07-06 | Technische Universität Wien | Verfahren zur herstellung von produkten auf basis von holz als rohstoff |
EP4023812A1 (de) * | 2020-12-29 | 2022-07-06 | MM BOARD & PAPER GmbH | Verfahren zur herstellung von produkten auf basis von holz als rohstoff |
CN113797175B (zh) * | 2021-09-08 | 2022-12-16 | 齐鲁工业大学 | 一种葡萄籽木质素纳米颗粒及其制备方法与在载药中应用 |
CN113855809B (zh) * | 2021-09-08 | 2022-12-27 | 齐鲁工业大学 | 一种将葡萄籽全转化至高附加值产品的工艺方法 |
CN114917351B (zh) * | 2022-06-07 | 2023-08-04 | 西南交通大学 | 一种基于木质素纳米管的药物载体及其制备方法 |
WO2024121306A1 (de) | 2022-12-07 | 2024-06-13 | Lignovations Gmbh | Emulsionen, kosmetische zusammensetzungen und sonnenschutzmittel |
EP4382088A1 (de) | 2022-12-07 | 2024-06-12 | Lignovations GmbH | Emulsionen, kosmetische zusammensetzungen und sonnenschutzmittel |
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Publication number | Priority date | Publication date | Assignee | Title |
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NZ538446A (en) | 2005-02-22 | 2008-01-31 | Mattersmiths Holdings Ltd | Compositions for use in treating lignocellulosic substances including wood |
WO2010026244A1 (de) | 2008-09-08 | 2010-03-11 | Basf Se | Verfahren zur integrierten herstellung von zellstoff und niedermolekularer wertstoffe |
GB0821419D0 (en) | 2008-11-24 | 2008-12-31 | Bio Sep Ltd | Processing of biomass |
WO2011037967A2 (en) * | 2009-09-25 | 2011-03-31 | Lake Michael A | Process for recovering lignin |
WO2011097720A1 (en) * | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd | Organosolv process |
CN102002165A (zh) | 2010-09-15 | 2011-04-06 | 东北林业大学 | 一种利用超临界反溶剂技术制备纳米木质素的方法 |
AP3271A (en) * | 2010-10-15 | 2015-05-31 | Upm Kymmene Corp | Continuous method for the precipitation of lignin from black liquor |
CN103459511A (zh) | 2011-03-24 | 2013-12-18 | 丽格诺创新有限公司 | 包含木质纤维素生物质和有机溶剂的组合物 |
BR112014022916B1 (pt) * | 2012-03-16 | 2020-11-24 | Valmet Power Ab | METODO PARA A SEPARAQAO DE LIGNINA A PARTIR DE LIXfVIA NEGRA |
KR101451299B1 (ko) * | 2012-03-26 | 2014-10-16 | 한국화학연구원 | 저회분 함량을 갖는 리그닌 입자의 제조방법 및 이에 의해 제조되는 저회분 함량을 갖는 리그닌 입자 |
FI127816B (en) * | 2012-06-06 | 2019-03-15 | Upm Kymmene Corp | Process for fractionating lignin |
US10233292B2 (en) * | 2012-12-07 | 2019-03-19 | National Technology & Engineering Solutions Of Sandia, Llc | Renewable aromatics from lignocellulosic lignin |
MY169121A (en) | 2013-03-15 | 2019-02-18 | Renmatix Inc | High purity lignin, lignin compositions, and higher structured lignin |
CN103145999A (zh) | 2013-03-26 | 2013-06-12 | 东北林业大学 | 一种粒径可控纳米木质素的制备方法 |
CN103254452B (zh) * | 2013-05-23 | 2014-10-29 | 广西大学 | 一种木质素纳米颗粒的制备方法 |
CN105829406B (zh) * | 2013-12-12 | 2020-06-30 | 索理思科技公司 | 木质素纳米颗粒分散体及制备和使用其的方法 |
EP3080353B1 (de) * | 2013-12-12 | 2022-01-26 | Annikki GmbH | Verfahren zur ligninreinigung und -isolierung |
FI126195B (en) * | 2014-01-28 | 2016-08-15 | Upm Kymmene Corp | Fiber-based product |
DE102014221238A1 (de) * | 2014-10-20 | 2016-04-21 | Mpg Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften E.V. | Verfahren zur Fällung von Lignin aus Organosolv-Kochlaugen |
CN104497322B (zh) | 2014-12-19 | 2018-02-09 | 中国林业科学研究院林产化学工业研究所 | 一种利用液相沉积技术制备纳米木质素的方法 |
WO2016197233A1 (en) | 2015-06-09 | 2016-12-15 | Universite Laval | Organosolv process for the extraction of highly pure lignin and products comprising the same |
JP6750832B2 (ja) * | 2015-09-25 | 2020-09-02 | 出光興産株式会社 | 精製リグニンの製造方法、精製リグニン、樹脂組成物及び成形体 |
CN106633967B (zh) * | 2016-09-14 | 2019-01-18 | 华南理工大学 | 一种二氧化钛/木质素基复合纳米颗粒及制备方法和应用 |
AT519535A1 (de) * | 2016-12-23 | 2018-07-15 | Univ Wien Tech | Herstellungsverfahren |
AT520087B1 (de) | 2017-04-19 | 2019-01-15 | Univ Wien Tech | Verfahren zur kontaktlosen Bestimmung von Strömungsparametern |
JPWO2019031610A1 (ja) * | 2017-08-10 | 2020-07-09 | 出光興産株式会社 | 改質リグニンの製造方法及び改質リグニン、並びに改質リグニン含有樹脂組成材料 |
CN107814952B (zh) * | 2017-10-18 | 2020-03-17 | 暨南大学 | 一种木质素纳米颗粒及同步载药的制备方法 |
US11524974B2 (en) * | 2017-10-26 | 2022-12-13 | Aalto University Foundation Sr | Aqueous lignin dispersions and methods of preparing the same |
US20210285155A1 (en) * | 2017-11-13 | 2021-09-16 | Sweetwater Energy, Inc. | Methods of making specialized cellulose and other products from biomass |
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