WO2020128034A1 - Procédés et systèmes de dissolution fractionnée de lignines dans un mode en flux continu segmenté - Google Patents

Procédés et systèmes de dissolution fractionnée de lignines dans un mode en flux continu segmenté Download PDF

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Publication number
WO2020128034A1
WO2020128034A1 PCT/EP2019/086784 EP2019086784W WO2020128034A1 WO 2020128034 A1 WO2020128034 A1 WO 2020128034A1 EP 2019086784 W EP2019086784 W EP 2019086784W WO 2020128034 A1 WO2020128034 A1 WO 2020128034A1
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Prior art keywords
lignin
solvent
functionalized
lignins
anyone
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PCT/EP2019/086784
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English (en)
Inventor
Claudia Crestini
Heiko Lange
Dimitris Argyropoulos
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Universita' Ca' Foscari
North Carolina State University
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Universita' Ca' Foscari
North Carolina State University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0215—Solid material in other stationary receptacles
    • B01D11/0219—Fixed bed of solid material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
    • B01D11/0265—Applying ultrasound

Definitions

  • the present invention relates to variously scalable continuous fractionation methods and systems applicable to isolated lignins and lignin-derivatives, including functionalized lignins and fractions of lignins as well as fractions of functionalized lignins.
  • lignocellulosic biomass Almost one third of the mass of lignocellulosic biomass is made of polyphenolic oligomers and polymers, which are, for the most part, lignins. 2 Since lignocellulosic biomass is already present in nature with a myriad of different specifics, 3 ⁇ 4 many industrial processes have been developed that are aimed at isolating the cellulose and hemi-cellulose parts of various types of lignocellulosic biomass. Many of these processes further modify the structure of the lignin component, which is often obtained as a rather low-quality by-product in biorefinery processes that were optimized with respect to obtaining/isolating the cellulose components.
  • Lignins produced from such processes are generally referred to in the industry as“technical lignins.”
  • Most technical lignins are used as additives in various low value applications, such as binders, dispersants, adhesives, and other fillers in various industrial applications.
  • Recently, bigger global players and promising newcomers in the biorefinery business have started to view the lignin-containing streams from these processes as an additional source for augmented revenues. 6
  • Fractionation of lignin can provide lignin fractions of variable molecular weight and functionality, and lignins isolated from these fractions exhibit or can be modified to exhibit an industrially acceptable polydispersity, variable functionality, and improved thermal stability amenable to use in some higher value applications.
  • conventional fractionation processes are batch-type processes and are not readily adaptable to providing a continuous run. The technical problem is that of overcoming the drawbacks of the prior art batch-type processes, thus providing a continuous run process for producing lignins.
  • the present invention concerns a system for continuous segmented flow-based fractional dissolution of lignins, functionalized lignins, fractions of lignins, and/or fractions of functionalized lignins, the system comprising at least the following components:
  • At least one solvent reservoir for containing at least one solvent effective to solubilize at least a portion of an isolated lignin material
  • the pump configured to pump the at least one solvent or mixture of solvents at a selectable flow rate against constant or variable back-pressure
  • the sample holder downstream from the pump, the sample holder configured to contain the isolated lignin material and solvent or mixture of solvents and configured to allow outflow of the solvent and solubilized lignin fractions while retaining insoluble fractions; at least one detector downstream from the lignin sample holder configured to detect organic material in a flowing solvent;
  • At least one collection vessel configured to collect a volume fraction of solubilized lignin in a solvent
  • tubing configured to connect the above components and to flow the solvent, mixture of solvents, and a mixture of one or more solvents and a solubilized lignin fraction.
  • this invention moreover provides a method of continuous segmented flow-based fractional dissolution of lignins, functionalized lignins or fractions of lignin or functionalized lignin through the system of anyone of claims 1-22 comprising:
  • lignin sample representing a lignin, a functionalized lignin or fraction of lignin or functionalized lignin;
  • the system uses the system to obtain one or more fractions of lignin from the isolated lignin sample representing a lignin, a functionalized lignin or fraction of lignin or functionalized lignin, wherein the one or more fractions of lignin have a difference in one or more of the following from the isolated lignin sample: weight average molecular weight, number average molecular weight, aromatic hydroxyl content, and heat stability.
  • FIGS. 1A-1C illustrate some lignin structures showing characteristic interunit bonding motifs and functional groups for different types of lignin: (A) branched polymeric lignin (outdated view); (B) linear chains of oligomeric milled wood lignin (MWL); 11 (C) complex structure of Lignoboost softwood kraft lignin (SWKL). 12 Not shown is the generic structures for lignosulfonates, since their structure is not yet fully understood.
  • FIGS. 2A-AD illustrate examples of different lignin fractionation processes: (A) typical work-flow for an ultrafiltration approach; 49 (B) typical work-flow for a fractional precipitation approach starting from a soluble fraction; 51 (C) typical work-flow of a chromatography-based fractionation, 52 (D) typical work flow of a fractionated solubilisation/filtration. 44
  • FIGS. 3A-B illustrate an embodiment of a continuous segmented flow system for fractional dissolution of lignins according to the present disclosure.
  • FIG. 3A is a schematic diagram of the system
  • FIG. 3B is a schematic diagram of an embodiment of column ends, showing an embodiment having fixed and adjustable endpieces.
  • FIG. 4 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), ASKL (small dash) and AIKL (large dash).
  • FIG. 5 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), MSKL (small dash) and MIKL (large dash).
  • FIG. 6 is a graph illustrating a comparison of GPC-elution profiles for PWL (solid), ASWL (small dash) and AIWL (large dash).
  • FIG. 7 is a graph illustrating a comparison of GPC-elution profiles for PWL (solid), MSWL (small dash) and MIWL (large dash).
  • FIG. 8 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), SKL fractions (various) and IKL (medium dash).
  • FIG. 9 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), SKL fractions (various) and IKL (medium dash).
  • FIG. 10 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), SWL fractions (various) and IWL (medium dash).
  • FIG. 11 is a graph illustrating a comparison of GPC-elution profiles for PWL (solid), SWL fractions (various) and IWL (medium dash).
  • FIG. 12 is a graph illustrating a comparison of GPC-elution profiles for PKL (solid), SKL fractions (various) and IKL (medium dash).
  • FIG. 13 is a graph illustrating a comparison of GPC-elution profiles for PWL (solid), SWL fractions (various) and IWL (medium dash).
  • FIG. 14 is a graph illustrating a comparison of GPC-elution profiles for PWL (solid), SWL fractions (various) and IWL (medium dash).
  • compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps (or analogs or derivatives thereof as discussed above). Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein.
  • Consisting essentially of” or “consists essentially” or the like when applied to methods and compositions encompassed by the present disclosure have the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments.
  • isolated means removed or separated from the native environment. Therefore, isolated lignin indicates the lignin is separated from its natural environment (e.g., plant source) but are not necessarily purified. For instance, an isolated lignin may be included in a byproduct from an industrial process or it may be subjected to additional purification and separation steps.
  • the term “technical lignin” indicates various lignins produced/isolated as a byproduct from various industrial processes such as, but not limited to physical and/or chemical processing of lignocellulose materials (e.g., for paper production, biofuel production, etc.).
  • Technical lignins can include, but are not limited to, lignosulphonates (LS) (from sulfite pulping), kraft lignins (KL) (from kraft pulping), organosolv lignins (OSL) (from processing with organic solvents), soda lignins (SL) (from soda pulping), etc.
  • LS lignosulphonates
  • KL kraft lignins
  • OSL organosolv lignins
  • SL soda lignins
  • “technical lignins” typically exhibit more variable polydispersity, higher reactivity, lower molecular weight, thermal instability than unprocessed lignin.
  • the term “functionalized lignins” includes all forms of chemically, biotechnologically, or physically altered or derivatized lignins on the basis of a fractional dissolution in various organic and/or aqueous solvents and/or mixtures thereof, homogeneous or heterogeneous under the employed flow conditions
  • AIKL acetone insoluble kraft lignin
  • AIWL acetone insoluble wheat straw lignin
  • ASKL acetone soluble kraft lignin
  • ASWL acetone soluble wheat straw lignin
  • ATR attenuated total reflectance
  • BPR back pressure regulator
  • CI-TMDP 2-chloro-4,4,5,5-tetramethyl-1 ,3,2-dioxaphospholane
  • DMF dimethyl formamide
  • DCM dichloromethane
  • DMAc dimethyl acetamide
  • DMSO dimethyl sulfoxide
  • GPC gel permeation chromatography
  • GVL g-valerolactone
  • HPLC high pressure liquid chromatography
  • HW hardwood
  • IKL insoluble kraft lignin
  • I R infrared
  • IWL insoluble wheat straw lignin
  • KL kraft lignin
  • LS kraft lignin
  • embodiments of the present disclosure in some aspects, relate to methods and systems for variously scalable continuous fractionation methods for isolated technical lignins and lignin- derivatives.
  • the methods and systems of the present disclosure can be run in continuous flow mode for increased efficiency and output of fractionated technical lignins.
  • LignoBoost lignin which is obtained by a novel process for the precipitation of lignin after standard kraft pulping, 8 and lignins obtained in industrialized organosolv pulping processes, e.g., Alcell lignin 9 and CIMV BioligninTM. 10
  • FIGS. 1A-1C Some characteristic structures of important types of lignins are shown in FIGS. 1A-1C, while Table 1 gives an overview over some characteristic key figures for various types of lignin.
  • Table 1 Important technical lignins and their main characterising features.
  • DMSO DMSO. HW, hardwood. SW, softwood. WS, wheat straw. RS, rice straw.
  • lignins While the functional groups play a significant role with respect to the type of application, the polymer characteristics are also important, especially the number average molecular weight (Mn) and the polydispersity (PD). Most isolated lignins are characterized by a polydispersity that a priori prevents any use in higher value applications, independent of the Mn, which additionally differs significantly depending on the isolation process. 5 One way to arrive at lignins that exhibit, at least, an industrially acceptable polydispersity is fractionation of lignin. This idea of fractionating lignins has been investigated on various samples since the 1980s, 36 after initial attempts in the early 1950s; 37 recently, however, it re-gained momentum in connection with more specified investigations for industrial applications of lignins.
  • Reported versions include sequential precipitation out of alkaline solutions, 38 fractional precipitation of re-dissolved kraft lignin in a gradually changed binary solvent system, 39 (sequential) extractions using different solvents 38 ⁇ 40- 46 or just plain water 47 followed by adsorption as well as the fractionation by ultrafiltration of black liquor using ceramic membranes 48-50 as versatile options.
  • FIGS. 2A-2D show flow diagrams of four common fractionation techniques: flow-based ultrafiltration, fractionated precipitation, chromatography-based fractionation, and fractionated solubilisation/filtration.
  • US20100170504A1 describes a biorefinery process for the fractionation of lignocellulosic biomass into cellulose, hemicellulose sugars, lignin, and acetic acid. Fermentable hemicellulose sugars, low-molecular-weight lignin, and purified acetic acid are also major products of the process and system, but the lignin is not further fractionated in this process. 55 None of the above-described processes are feasible on a large scale in a continuously run process.
  • one purpose of the methods of the present disclosure is to provide a process for fractionation of technical lignins that is adaptable to a continuous flow model.
  • the process of fractionated precipitation can be inverted, inversed, and transferred into a segmented flow chemistry set-up to become a continuous process of fractionated dissolution that can be fully automated and run continuously.
  • the methods of the present disclosure are scalable by optimization of the dimensions of the set-up as well as the overall run time.
  • the methods and systems of the present disclosure relate to the fractionation of technical lignins in a scalable and continuous fashion.
  • methods of the present disclosure are referred to herein as “continuous segmented flow-based fractional dissolution of lignins”.
  • the system for continuous segmented flow-based fractional dissolution of lignins of the present disclosure includes at least the following elements: a pump, and lignin-sample holder, at least one detector capable of detecting organic material in a solvent stream, and one or more collection vessels.
  • An embodiment of a system 10 of the present disclosure is illustrated in FIG. 3A, showing a pump module 20, a lignin sample holder module 30 (including a number of lignin sample holders 32, a detector module 40, and a collection module 50.
  • the pump module 20 includes at least one pump 22 suitable for pumping various solvents as well as solvents mixed with various lignin fractions.
  • the pump is capable of pumping at various flow rates and against various back-pressures.
  • the solvents to be pumped can include a single solvent (e.g., a pure solvent), and in embodiments, the solvents can include freely selectable miscible and/or immiscible mixtures of two or more solvents. As shown in FIG. 3A, the solvents can be contained in solvent reservoirs 24 and fed to or drawn by the pump 22 from the one or more solvent reservoirs 24 via tubing 26.
  • the lignin-sample holder module 30 is placed downstream to the pump module 20 (in embodiments, immediately downstream from the pump 22).
  • the lignin sample holder module includes one or more sample holders 32 is configured to hold lignin sample materials, such as technical lignins.
  • the sample holder is made of materials compatible with the solvents chosen for the dissolution protocol and suitable to withstand the backpressures generated in the system.
  • the lignin-sample holder can be one or more columns 32, such as the column illustrated in FIG. 3B and described in greater detail below.
  • the sample holder(s) 30 can be housed in an oven 34.
  • the term“columns” may be used interchangeably with“lignin sample holder;” however, it will be appreciated by the skilled artisan, that containers other than column-shaped containers can be used in embodiments of the present disclosure.
  • the sample can flow from the pump 20 to the sample holders/columns 32 via tubing 26 and from the sample holders to the one or more detectors 42 via tubing 36.
  • the detector module 40 includes an in-line detector 42 or a series of one or more detectors.
  • the detector is placed downstream to the lignin sample holder.
  • the detector is suitable for the facile detection of organic material in the flowing solvent.
  • the organic material detected can be UV-active or UV-inactive material, or a combination.
  • the detector is also in data communication with a controller 44, as described in greater detail below.
  • the collection module 50 includes one or more collection vessels 52 configured for collecting various volume fractions and placed downstream to the detector(s) 42.
  • the system includes two or more collection vessels, and each is configured to collect a different fraction of lignin.
  • the at least a portion of the technical lignins in the sample can display certain characteristics such as, but not limited to the following.
  • the technical lignins have solubility in at least one solvent, such as, but not limited to, an organic solvent, a water-based solvent, an ionic liquid solvent, or a combination thereof.
  • the technical lignins can have an average molecular weight ranging from 180 to 1000000 Da.
  • the technical lignins can have impurity contents of up to 80%, with impurities being selected from organic substances, inorganic substances, and mixtures thereof. Depending on the conditions selected, fractionation can be achieved and fractions released by one or more of the following:
  • the system allows monitoring of lignin fractions in real time and inline by one or more of the following: a photo diode array (PDA) detector; an attenuated total reflectance (ATR) infrared (IR) detector; a refractive index (Rl) detector; and a multi angle laser light scattering (MALLS) detector.
  • PDA photo diode array
  • ATR attenuated total reflectance
  • IR infrared
  • Rl refractive index
  • MALLS multi angle laser light scattering
  • the system includes at least the PDA detector.
  • the system includes the PDA detector and ATR IR detector.
  • the system includes at least the PDA detector and one or more of the ATR I R detector, the Rl detector, and/or the MALLS detector.
  • the system is monitored and controlled using a computer (e.g., personal computing device or other computing device) equipped with suitable software.
  • a computer e.g., personal computing device or other computing device
  • suitable software e.g., software that was used to control the process.
  • the process was found to be easily adopted to accommodate fractionation and/or purification of chemically or biotechnologically altered lignins from industrial and laboratory productions.
  • the system of the present disclosure includes a solvent delivery module for transporting solvents used for the fractionated dissolution protocol from solvent reservoirs into the system.
  • This module is referred to herein as a“pump” and may include one or more pumps 22.
  • the material of the pump(s) 22 is compatible with the solvents and/or solvent systems used and compatible with the chemical and physical conditions attributable to dissolved lignin solutions in the chosen set-up and system.
  • the pump can be a conventional HPLC piston pump, a peristaltic pump, or even a simple syringe pump so long as the pump is strong enough to work against the back pressure generated by the system and the lignin-filled column.
  • the materials of the pump are compatible with the solvents used.
  • a pump of the present disclosure can be made of various materials, depending on the construction, such as, but not limited to, stainless steel, chromium, rubber for seals, plexiglas components and other suitable materials.
  • the pump is configured for pumping at various flow rates against changeable back-pressures.
  • the pump is configured to furnish isocratic or gradient flows of solvent systems including at least one solvent suitable to dissolve lignin molecules. Bothe isocratic and gradient flows of solvent systems can vary in flow rate during the fractional dissolution protocol at various flow rates.
  • the pump is in communication with and can be controlled by a computer-assisted controller unit 44 that allows read-out and real-time remote operation and/or changes of crucial parameters such as, but not limited to: the pressure the pump has to work against, the flow rate, the solvent mixture, etc.
  • the computer-assisted controller unit allows real-time changes of flow-rates and current solvent mixture.
  • the pump is a mechanical pump, such as, but not limited to, a piston pump.
  • the pump is equipped with a suitable degasser unit capable of providing solvents substantially free of gas bubbles.
  • the pump module can also include a mixing element that can mix the solvents coming from the pumps.
  • the mixing element can also be in communication with the controller 44 to control mixing speed, time, etc.
  • Module column (lignin sample holder module 30): The system of the present disclosure also includes at least one lignin sample holder 32 in which a weighted quantity of isolated lignin can be loaded in dry form.
  • the lignin sample holder is a column, but may take the form of other containers as well.
  • the column does not include an inert filler material to be mixed with the lignin.
  • the lignin sample holder is also referred to as a column. In embodiments, as illustrated in FIG.
  • the column 32 is closed at one end (e.g., a bottom end) with a dedicated invariable/fixed end-piece 33 that is configured to prevent lignin particles from clogging the tubing.
  • the other end of the column is closed with an adjustable end-piece 35 that is configured to prevent lignin particles from clogging the tubing.
  • the end-pieces provide mechanically robust connection ports to attach the tubing.
  • the sample holders/columns are made of materials such as, but not limited to, glass or stainless steel, or other material suitable to withstand the chemical and physical demands posed by the chosen fractional dissolution protocol.
  • the invariable and variable end-pieces allow incorporation of a non-filtering solid porous material.
  • such non-filtering solid porous material can be a frits made from PTFE, PVF, cellulose, regenerated cellulose, ceramics, silicates.
  • the variable endpiece is adjusted in such a way that the lignin in the column is densely packed. Adjustment can be optimized during fractionated dissolution runs.
  • invariable and variable end-pieces allow incorporation of a filtering solid porous material.
  • the invariable and variable end-pieces allow additional incorporation of and/or a dialysis filter membrane as well.
  • the adjustable endpiece gains its adjustability by a screw mechanism, which can be a remotely controllable screw mechanism (controlled by, e.g., the controller 44).
  • sample holders/columns 32 can be housed inside a heatable chamber, herein called a column oven 34.
  • the temperature setting of the column oven can be realised remotely in real-time (by, e.g., the controller 44).
  • the columns 32 can instead be submerged in an ultrasonication bath instead of a column oven, such as to assist dissolution by sonication during segmented continuous flow fractional dissolution.
  • the system also includes one or more controllable switch points 38 (also referred to herein as“column dialers”).
  • a plurality of packed columns 32 are connected to a main flow line (e.g., tubing) using two remotely controllable switch points/column dialers 38, placed before/upstream of the column(s) 32 and one after/downstream of the columns.
  • each column dialer can be remotely controlled (e.g., by controller 44), including control on the basis of real-time detector signalling.
  • the column dialers also allow manual control.
  • Module detector (40) Downstream of the column-module 30, systems of the present disclosure include at least one or a series of detectors 42.
  • the detectors are located inline with the sample holder module 30.
  • the detectors 42 are able to monitor contents in the liquid sample stream exiting the column.
  • the detector can include one or more types of detectors configured for i) detecting lignin (purified or in the presence of other biomass compounds and/or in the presence of inorganic or organic impurities), including, for example monomeric, oligomeric, and polymeric species, and/or ii) allowing a monitoring of the concentration of a specific component in the stream of liquid exiting the column.
  • detector cells can be heated.
  • a combination of PDA- and Rl-detectors can be included.
  • a combination of PDA- and ATR-IR-detectors are used.
  • a combination of PDA- and ATR-IR- and MALLS-detector is used.
  • one or more detectors 42 are linked to a controller 44 (e.g., a computer), which communicates detection results in real time in a way that allows real-time feedback for pump control.
  • the system can also include one or more back pressure regulators 46.
  • the sample/column module 30 is facultatively followed by a device for controlling overall system pressure, called a back pressure regulator (BPR).
  • BPR back pressure regulator
  • the BPR allows adjustment of overall system pressure, which can allow maintenance of any solvent system chosen for fractionated dissolution in the liquid state, even when the fractionation is run at temperatures higher than the boiling points of the solvents used or any positive azeotrope a given solvent system may form inside the system.
  • a facultative first BPR is installed between the sample columns 32 and the detector 42 in case column operating pressures override maximum pressure limits of downstream located detector modules.
  • the detector module 40 can be followed by a device for controlling overall system pressure, which is referred to herein as a closing back pressure regulator (closing BPR).
  • a closing BPR can be included downstream of the one or more detectors 42.
  • a closing BPR allows adjustment of overall system pressure to maintain any solvent system chosen for fractionated dissolution in the liquid state even when the fractionation is run at temperatures higher than the boiling points of the solvents used or any positive azeotrope a given solvent system may form inside the set up.
  • the system can include both a facultative BPR and a closing BPR. In such embodiments, the closing BPR is chosen in such a way that it does prevent any liquid from entering in a gaseous state in the detector module while only adding a minimum of additional pressuring to the entire system used for fractional dissolution.
  • Module collection Downstream from the detector module 40 and optional closing BPR 46, the system includes a collection module 50 having one or more collection vessels 52 configured for collecting several individual batches of liquid of variable volume including solubilized lignin fractions.
  • the collection module 50 may also be referred to herein as the“fraction collector.”
  • the fraction collector is remotely controlled by a computer-assisted system (e.g., the controller 44) that allows real-time reaction of the fraction collector to respond to the real-time monitored detector signals. For instance, in response to a signal from the detector 42 that a different fraction is being pumped through the system, the controller could signal to direct the flow to a different collection vessel 52.
  • Tubing Connection of various modules is provided by conduit (also referred to herein as tubing), to convey the lignin samples/fractions from one module to the next.
  • conduit also referred to herein as tubing
  • tubing 26 carries lignins samples from the sample reservoirs to the pump and then carries lignin samples from the pump 22 to the columns 32. Then, the samples of solubilized lignin exit the columns 32 and proceed to the detector 42 via tubing 36, and from the detector to the fraction collection vessels 52 via tubing 36.
  • the tubing has appropriate chemical and physical characteristics sufficient to withstand the physical and chemical demands set by the fractionated dissolution set-up.
  • the tubing includes various types of appropriate connectors, more-way valves, switches, stop cocks.
  • the tubing material is chosen from the group including, but not limited to, stainless steel tubing, PEEK-tubing, PTFE-tubing or combinations.
  • the inner diameters of the tubing are chosen in such a way that the tubing as such does not cause additional pressuring of the system.
  • tubing junctions are constructed in such a way that undesired clogging of tubing is minimized (e.g., by providing a mesh or sieve at various inlets and outlets between the modules described above, see for example, FIG. 3B).
  • the system of the present disclosure provides many advantages, such as the ability to operate in continuous mode, to use two or more solvents or mixtures thereof at one time, to provide multiple columns in order to process more than one lignin sample at a time, to provide real time control of the concentration of solvent, real-time control of the direction and rate of flow, to allow real-time control of system pressure, to provide real-time monitoring of the fractions being obtained and collected, to allow remote control of automated fraction collection, and so forth.
  • the system of the present disclosures is configured, with the pumps, tubing, optional switches, back flow regulators, and other components such that it can be operated where the direction of flow of the solvent stream is in an anti-gravitational direction.
  • the solvents used in the system can be used under critical conditions.
  • isolated lignin that has not been chemically and/or physically and/or biotechnologically and/or biologically altered after initial isolation: (a) has a number average molecular weight (M n ) of from 250 Da to 100000 Da, as for example determined by GPC as described below; and (b) has a molar ratio of aromatic hydroxyl content to aliphatic hydroxyl content in the range of from 30/1 to 1/30 as for example determined by quantitative 31 P NMR as described below.
  • the lignin includes from 0 mmol/g to 8 mmol/g aromatic hydroxyl content as determined by quantitative 31 P NMR as described below.
  • the lignin displays solubility against at least one organic or aqueous phase-based solvent and/or solvent system at physical conditions realizable in the above-described system of the present disclosure (this includes explicitly super-critical solvents).
  • the lignin displays solubility against at least one organic or aqueous phase-based solvent and/or solvent system at physical conditions realizable in the above-described system of the present disclosure (this includes explicitly super critical solvents).
  • the lignin material to be fractionated in the systems and methods of the present disclsoure is used in the provided form and is not mixed with additional inert mateirals, and the like.
  • Organic solvents can be used as single solvent or in various combinations including one or more solvents in various volume ratios.
  • Some typical solvents include but are not limited to: i) protic polar solvents like acetic acid, formic acid, methanol, ethanol, propanol; ii) aprotic polar solvents like acetone, tetrahydrofurane, g-valerolactone, diethyl ether, methyl tert- butyl ether, dioxane, dichloromethane, trichloromethane, tetrachloromethane, chlorinated ethanes and propanes; iii) apolar aprotic solvents like pentane, hexane, cyclohexane; iv) aromatic solvents like toluene, xylenes, mesitylene, halogenated benzenes; and v) solvents from the groups of aliphatic and aromatic /
  • Various physical characteristics of a single solvent or mixtures of solvents determine a priori or real-time adjustments to the system appropriate for fractionated dissolution. It is noted that adequate choices of BPRs allow use of solvents and solvent mixtures, including those forming negative azeotropes, under critical conditions such as to avoid gas formation in the lines.
  • High viscosity organic solvents e.g., dimethylsulfoxide (DMSO), A/./V-dimethyl formamide (DMF), A/./V-dimethyl acetamide (DMAc), g-valerolactone (GVL) can be used utilizing heatable but otherwise analogously working equipment.
  • solvents can be combined homogeneously in any ratio while in liquid state under the conditions applied for the fractionated dissolution.
  • solvent mixtures can be recycled during isolation of dissolved fractionated lignin.
  • solvents can be separated.
  • solvent mixtures can be recycled as mixture with variations in volume ratios compared to starting mixes not exceeding 2%.
  • fractional dissolution of lignins can be realised in methods and systems of the present disclosures using water-based solvent systems of various pH and/or various salinity and/or various Lewis acidity or basicity and/ orvarious ratios and concentrations of chaotropic and kosmotropic salts, wherein chaos- and kosmotropic refers to characteristics described by Hofmeister (incorporated by reference herein).
  • fractionation hardware set-ups can resemble the following illustrative example: fractional dissolutions are performed using a Shimadzu instrument including a controller unit (CBM-20A), a pumping unit (LC 20AT), a degasser unit (DGU-20A3), a column oven (CTO-20AC), a photo diode array detector (SPD-M20A), and a refractive index detector (RID-10A).
  • the instrumental set-up can be controlled using the Shimadzu LabSolution software package (Version 5.42 SP3).
  • a known quantity of a solid dry lignin is placed in a column that is closed at one end with a fixed endpiece. After filling, the column is closed at the other end using an adjustable endpiece. Both endpieces are equipped with a porous frit or membrane made of a material that is compatible with the desired fractionation protocol in order to prevent escape of solid lignin particles into the tubing.
  • the column can placed in a column holder inside a column oven, in an oil bath or other environment for even heat distribution; however, in embodiments where heat is not needed, no oven, etc. is needed.
  • the tubing is connected in a manner to line-up the various columns.
  • a simple set-up of chosen modules as described above are arranged in the following order: degaser - pump- column dialer in column oven - single column in column oven - column dialer in column oven- PDA detector - Rl-detector - back pressure regulator - fraction collector.
  • the desired solvent gradient system is programmed, and the segmented continuous fraction is started. Fractions are collected according to absorbance signal changes monitored by the inline PDA- and Rl-detectors. During the process, some losses of solid mass inside the column are compensated by adjusting the via a screw mechanism adjustable endpiece in a way that the remaining solids stay densly packed inside the column.
  • fractions can be concentrated and solvent can be recycled.
  • solid remains in the column are collected as insoluble fraction. Once dried, fraction yields are determined. Obtained fractions are analysed at least by means of GPC and quantitative 31 P NMR.
  • M n and M w The number average molecular weight, M n , as well as the weight average molecular weight, M w , can be determined using gel permeation chromatography (GPC). Briefly described, lignin samples are dissolved in HPLC-grade dimethylsulfoxide (DMSO) (Chromasolv®, Sigma-Aldrich) containing 0.1 % (m/v) lithium chloride (LiCI) and filtered over a 0.45 pm syringe filter prior to injection into a 20 pL sample loop.
  • DMSO dimethylsulfoxide
  • LiCI lithium chloride
  • T ypical analysis set-ups resemble the following specific example: GPC-analyses are performed using a Shimadzu instrument consisting of a controller unit (CBM-20A), a pumping unit (LC 20AT), a degasser unit (DGU-20A3), a column oven (CTO-20AC), a diode array detector (SPD-M20A), and a refractive index detector (RID-10A); the instrumental set-up is controlled using the Shimadzu LabSolution software package (Version 5.42 SP3).
  • an analytical GPC column PLgel 5 pm MiniMIX-C column (Agilent, 250 c 4.6 mm) is used.
  • M n is calculated according to the formula in which M n is the number average molecular weight
  • V being the volume of the curve over a given logM interval d(logM).
  • M j is a given molecular weight.
  • M w is calculated according to the formula in which M w is the number average molecular weight
  • V being the volume of the curve over a given logM interval d(logM).
  • M j is a given molecular weight.
  • Typical spectral parameters for quantitative studies are as follows: 90° pulse width and sweep width of 6600 Hz.
  • the spectra are accumulated with a delay of 15 s between successive pulses. Line broadening of 4 Hz is applied, and a drift correction is performed prior to Fourier transform.
  • Chemical shifts are expressed in parts per million from 85 % H3PO4 as an external reference. All chemical shifts reported are relative to the reaction product of water with CI-TMDP, which has been observed to give a sharp signal in pyridine/CDCI 3 at 132.2 ppm. To obtain a good resolution of the spectra, a total of 256 scans are acquired. The maximum standard deviation of the reported data is 0.02 mmol/g, while the maximum standard error is 0.01 mmol/g. 58
  • Quantification on the basis of the signal areas at the characteristic shift regions is done using a tailor-made table calculation in which the abundances, given in mmol/g, of the different delineable phosphitylated hydroxyl groups are determined on the basis of the integral obtained for the signal of the internal standard, that is present in the analysis sample at a concentration of 0.1 m, creating a signal at the interval ranging from 152.2 ppm to 151.6 ppm.
  • the area underneath the peak related to the internal standard is set to a value of 1.0 during peak integration within the standard processing of the crude NMR data, allowing for determining abundances using simple rule-of-proportion mathematics under consideration of the accurate weight of the sample used for this analysis.
  • the analysis is run in triplicate, and final values are obtained as the standard average.
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a concentration range of “about 0.1 % to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1 %, 2%, 3%, and 4%) and the sub ranges (e.g., 0.5%, 1.1 %, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the term“about” can include traditional rounding according to significant figures of the numerical value.
  • the phrase“about‘x’ to‘y’” includes“about‘x’ to about‘y’”.
  • EXAMPLE 1 Segmented continuous flow fractionation of a softwood kraft lignin using isocratic flow of acetone at room temperature
  • acetone soluble kraft lignin (ASKL) is isolated from the acetone fraction by distilling of the acetone; recovered acetone could be used for consecutive fractionation runs.
  • Acetone insoluble kraft lignin (AIKL) is recuperated from the column and air-dried.
  • FIG. 4 shows the overlay of the GPC races
  • Table 2 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 2 Numerical data for GPC and 31 P NMR analysis of softwood kraft lignin fractions obtained in isocratic flow using acetone as single solvent.
  • EXAMPLE 2 Segmented continuous flow fractionation of a softwood kraft lignin using isocratic flow of methanol at room temperature
  • MLKL methanol soluble kraft lignin
  • MIKL Methanol insoluble kraft lignin
  • Table 3 Numerical data for GPC and 31 P NMR analysis of softwood kraft lignin fractions obtained in isocratic flow using methanol as single solvent.
  • EXAMPLE 3 Segmented continuous flow fractionation of a wheat straw organosolv lignin using isocratic flow of acetone at room temperature
  • a commercialised wheat straw organosolv lignin WL
  • WL commercialised wheat straw organosolv lignin
  • this organosolv lignin is fractionated in segmented continuous flow mode at room temperature using acetone as single solvent, using an isocratic flow at 0.2 ml/min for 420 min, corresponding to 84 mL of solvent in total.
  • acetone soluble wheat straw organosolv lignin (ASWL) is isolated from the acetone fraction by distilling of the acetone; recovered acetone could be used for consecutive fractionation runs.
  • Acetone insoluble wheat straw organosolv lignin (AIWL) is recuperated from the column and air-dried.
  • FIG. 6 shows the overlay of the GPC traces, and Table 4 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy after phosphitylation using 2-CI- TMDP. Table 4: Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in isocratic flow using acetone as single solvent.
  • EXAMPLE 4 Segmented continuous flow fractionation of a wheat straw organosolv lignin using isocratic flow of methanol at room temperature
  • a commercialised wheat straw organosolv lignin WL
  • WL commercialised wheat straw organosolv lignin
  • this organosolv lignin is fractionated in segmented continuous flow mode at room temperature using acetone as single solvent, using an isochratic flow at 0.2 ml/min for 300 min, corresponding to 60 mL of solvent in total.
  • MSWL methanol soluble wheat straw organosolv lignin
  • MIWL Methanol insoluble wheat straw organosolv lignin
  • Table 5 Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in isocratic flow using acetone as single solvent.
  • kraft lignin 1 g of a commercialised softwood kraft lignin (KL) are placed in a glass column equipped with one fixed and one adjustable endpiece carrying porous polytetrafluoroethylene frits.
  • KL commercialised softwood kraft lignin
  • FIG. 8 shows the overlay of the GPC traces
  • Table 6 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 6 Numerical data for GPC and 31 P NMR analysis of softwood kraft lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • a commercialised softwood kraft lignin KL
  • KL commercialised softwood kraft lignin
  • FIG. 9 shows the overlay of the GPC traces, and table 7 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 7 Numerical data for GPC and 31 P NMR analysis of softwood kraft lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • EXAMPLE 7 Segmented continuous flow fractionation of a wheat straw organosolv lignin using a gradient elution of hexane-acetone at room temperature
  • a commercialised softwood kraft lignin WL
  • FIG. 10 shows the overlay of the GPC traces, and Table 8 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 8 Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • EXAMPLE 8 Segmented continuous flow fractionation of a wheat straw organosolv lignin using a gradient elution of hexane-acetone at elevated temperature
  • a commercialised wheat straw organosolv lignin WL
  • Table 9 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy
  • Table 9 Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • EXAMPLE 9 Fast Segmented continuous flow fractionation of a softwood kraft lignin using a gradient elution of hexane-acetone at elevated temperature
  • a commercialised softwood kraft lignin KL
  • KL commercialised softwood kraft lignin
  • FIG. 12 shows the overlay of the GPC traces, and Table 10 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 10 Numerical data for GPC and 31 P NMR analysis of softwood kraft lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • EXAMPLE 10 Fast Segmented continuous flow fractionation of a wheat straw organosolv lignin using a gradient elution of hexane-acetone at elevated temperature
  • a commercialised wheat straw organosolv lignin WL
  • FIG. 13 shows the overlay of the GPC traces, and Table 11 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 11 Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.
  • a commercialised wheat straw organosolv (WL) are placed in a glass column equipped with one fixed and one adjustable endpiece carrying porous polytetrafluoroethylene frits.
  • this organosolv lignin is fractionated in segmented continuous flow mode at room temperature using the following pure solvents at room temperature at a constant flow rate of 0.75 ml/min in the given order: diethyl ether (Et 2 0), dichloromethane (DCM), methanol (MeOH); total run-time was 12 min Et20, 32 min DCM and 56 min MeOH, corresponding to a total of 75.5 mL of solvent used.
  • FIG. 14 shows the overlay of the GPC traces, and Table 12 lists data for M n and M w and abundancies of hydroxyl groups as determined by quantitative 31 P NMR spectroscopy.
  • Table 12 Numerical data for GPC and 31 P NMR analysis of wheat straw organosolv lignin fractions obtained in flow using a gradient elution system comprised of hexane-acetone mixtures.

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Abstract

L'invention concerne un système et un procédé de dissolution fractionnée basé sur un flux continu segmenté de lignines, de lignines fonctionnalisées, de fractions de lignines et/ou de fractions de lignines fonctionnalisées.
PCT/EP2019/086784 2018-12-21 2019-12-20 Procédés et systèmes de dissolution fractionnée de lignines dans un mode en flux continu segmenté Ceased WO2020128034A1 (fr)

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