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    • 专利摘要:
    METHOD FOR OBTAINING CARBONIZED LIGIN. The present invention relates to a method for obtaining stabilized lignin having a defined granulometric distribution from a lignin-containing liquid, whereby, before and/or during hydrothermal carbonization, the H+ ion concentration of a lignin-containing liquid is adjusted. so that the granulometric distribution of the hydrothermal carbonized lignin is obtained, and that it can be separated from the liquid containing the carbonized lignin and can be optionally purified.
    公开号:BR112017002606B1
    申请号:R112017002606-6
    申请日:2015-08-04
    公开日:2022-02-01
    发明作者:Tobias Wittmann
    申请人:Suncoal Industries Gmbh；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The invention relates to a method for obtaining a stabilized lignin with granulometric distribution from a lignin-containing liquid in which the ionic concentration of H+ of a lignin-containing liquid before and/or during hydrothermal carbonization is such adjusted form that the desired granulometric distribution of the hydrothermally carbonized lignin is obtained and this can be separated from the liquid containing the carbonized lignin or optionally purified. DEFINITIONS Liquid containing lignin
    [002] A liquid containing lignin is hereinafter understood to be a liquid, preferably water, which contains lignin, wherein the lignin is either dissolved and/or may be present as a filterable solid substance. Preferably, in the case of the lignin-containing liquid of residual bleach resulting from the fractionation process for biomass, for example, a Kraft process or a potassium hydroxide process. If, in the case of the lignin-containing liquid, it is residual lye resulting from a fractionation process, then the pH value of the lignin-containing liquid will generally be in the neutral or alkaline range in general at a pH value > 7.
    [003] In addition, in the case of the lignin-containing liquid, it is a liquid containing the lignin-containing residue resulting from a hydrolysis, for example, a thermal hydrolysis, an enzymatic hydrolysis or an acid-catalyzed hydrolysis, being that the lignin-containing residue resulting from the hydrolysis is preferably drained first and the filter cake thus obtained or the concentrate thus obtained is then mixed with a liquid and together with this forms the lignin-containing liquid, which is conducted to the process according to the invention. If the lignin-containing liquid is the lignin-containing residue resulting from hydrolysis, then the pH value, when the lignin-containing residue is mixed with distilled water after drainage, will generally be in the neutral or acidic range, generally at a pH value < 7.
    [004] The liquid containing lignin, in addition to lignin, may also contain other organic and inorganic components. Characteristic for the lignin-containing liquid is that the lignin content in the organic dry mass is above 50%, especially above 60% or even above 70%, and therefore well above the lignin content of woody biomass, which is stands at 15%-35%. By lignin content below is meant the sum of Klason lignin and acid-soluble lignin. In this case, the quantity and percentage indications for lignin always refer to the ash-free dry mass. stabilized lignin
    [005] Lignin, which has been subjected to a hydrothermal carbonization according to the method according to the invention at a temperature in a range of approximately 150°C to approximately 280°C, for example, in a temperature range between 180°C and 280°C, especially in a temperature range between 190°C and 250°C and especially in a temperature range between 190°C and 250°C, is hereinafter referred to as stabilized lignin. Stabilized lignin is also called carbonized lignin. Liquid containing carbonized lignin
    [006] Liquid, which contains carbonized lignin after hydrothermal carbonization, wherein the carbonized lignin may be present or dissolved and/or as a filterable solid substance in the liquid, is hereinafter designated as liquid containing carbonized lignin. Dissolved lignin / dissolved carbonized lignin
    [007] Lignin will hereinafter be referred to as lignin dissolved in the liquid containing lignin or as carbonized lignin dissolved in the liquid containing carbonized lignin, when it is not possible to carry out a separation by means of a filtration through a filter paper with a pore size < 10 μm arising from the liquid containing lignin or from the liquid containing carbonized lignin. Undissolved lignin / carbonized undissolved lignin
    [008] Lignin will hereinafter be designated as undissolved lignin in the liquid containing lignin or as carbonized lignin not dissolved in the liquid containing carbonized lignin, when it is possible to carry out the separation by filtration through a filter paper with a pore size < 10 μm resulting from lignin-containing liquid or carbonized lignin-containing liquid. Dissolved lignin precipitation / dissolved carbonized lignin deposit
    [009] By precipitation or sedimentation is hereinafter meant a predominant transfer of greater than 40%, preferably greater than 50%, even more preferably greater than 60%, especially preferably greater than 70% of dissolved lignin or carbonized lignin dissolved in unsaturated lignin. dissolved or in undissolved carbonized lignin. dry pasta
    [010] The dry mass is the residue of evaporation of a liquid, obtained in the case of an evaporation under ambient pressure of 105°C until the constancy in weight. organic dry pasta
    [011] The organic dry mass is the dry mass minus the remaining ash in the case of incineration at 815°C until weight constant. Particle size distribution
    [012] It is understood by granulometric distribution following the Q3 distribution. The measurement of the granulometric distribution of lignin or carbonized lignin is carried out in a suspension by means of laser diffraction without prior drying of the lignin or carbonized lignin. Before and/or during the measurement of the particle size distribution, the sample to be measured is dispersed with ultrasound so that a stable particle size distribution is obtained through several measurements. Colloidal carbonized lignin
    [013] By colloidal carbonized lignin it should be understood below a suspension resulting from carbonized lignin in a liquid, and the carbonized lignin does not form a sediment with a dry substance content > 1% in the liquid, but is divided in the form homogeneous. The homogeneous distribution of the carbonized lignin in the liquid is achieved through a sufficiently strong polarity of the carbonized lignin particle. The D90 of the particle size distribution of colloidal carbonized lignin is generally less than 60 μm and the D50 is generally less than 20 μm. In the case of sufficient dispersion with ultrasound, the D90 of the carbonized colloidal lignin particle size distribution is generally less than 30 μm, the D50 is generally less than 10 μm. The granulometric distribution of colloidal carbonized lignin is generally unimodal. Carbonized lignin sediment
    [014] A carbonized lignin sediment forms when the polarity and/or particle size distribution of carbonized lignin is implemented such that at least 90% of the carbonized lignin forms under the force of gravity within at most 5 minutes a layer of sediment.
    [015] It is understood by carbonized lignin fine sediment the fact that the D90 of the particle size distribution is less than 1000 μm. In an example embodiment the D90 of the particle size distribution is less than 100 μm, especially less than 50 μm. The particle size distribution of fine sediment carbonized lignin can be compared to that of colloidal carbonized lignin. The difference between a colloidal carbonized lignin and a carbonized lignin fine sediment lies in the fact that the difference with colloidal lignin forms at least 90% of the carbonized lignin fine sediment with a dry substance content > 1% under the action of force of gravity within a maximum of 5 minutes a layer of sediment.
    [016] Coarse sediment is understood to mean that the D90 of the particle size distribution is more than 1000 μm. DESCRIPTION OF THE INVENTION
    [017] Lignin precipitates as a by-product of woody biomass fractionation processes.
    [018] During fractionation processes the lignin is either typically placed in solution and then separated from the non-soluble components of the woody biomass (e.g. Kraft process) or the woody biomass is de-polymerized so that the lignin remains largely as solid substance (eg hydrolysis process). Lignin is present, therefore, according to the type of fractionation process or dissolved in a liquid or as a solid substance.
    [019] According to the state of the art, lignin that is dissolved in a liquid containing lignin can be precipitated by increasing the ionic concentration of H+. Furthermore, it is known that by conducting this precipitation process, especially by selectively adapting the pH value, the ionic strength and the residence time, it can exert an influence on the granulometric distribution of the precipitated lignin. (Patent Document WO 2012/177198 A1 , WO 2013/070130A1 ). Lignin, which was obtained by precipitation from a liquid obtained containing dissolved lignin, shows a thermoplastic behavior according to the state of the art (patent document US 2013/0116383 A1). A fundamental disadvantage of such a product is that it plastically deforms upon heating and is not temperature stable. The use of such lignin is therefore restricted to applications in which temperatures of 80°C are generally not exceeded.
    [020] According to the state of the art, an attempt is made to overcome the thermoplastic property of lignin by heating it under inert conditions, for example, using nitrogen, helium, neon, argon, krypton or xenon through stabilization (document patent WO 2013/112100 A1). A fundamental disadvantage of such a process is the focus on the application of carbon fibers as well as the high costs for stabilization.
    [021] Furthermore, it is known that lignin can be prepared through hydrothermal carbonization at temperatures above 300°C for substitution by plastic material (patent document JP 2011-178851 A). The fundamental disadvantage of such a method is the high process temperature. Furthermore, it is not clear how in such a variant of hydrothermal carbonization one can influence the particle size distribution. Furthermore, it is unclear whether lignin that has been treated according to the method described in patent document JP 2011-178851 A has lost its thermoplastic behavior.
    [022] It is the task of the invention to remedy the disadvantages of the state of the art with the use of lignin and improve the obtaining of lignin with a granulometric distribution.
    [023] The task is solved through a method according to the invention for obtaining stabilized lignin with defined granulometric distribution from a liquid containing lignin, in which
    [024] - the liquid containing lignin under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C and 250°C, is subjected to a hydrothermal carbonization in which the lignin is converted into a carbonized lignin,
    [025] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization and
    [026] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [027] Within the scope of a method according to the invention, therefore, stabilized lignin is obtained from a liquid containing lignin, the granulometric distribution of the stabilized lignin is adjusted and the stabilized lignin is separated from the liquid containing the stable lignin. If necessary, the stabilized lignin is further purified.
    [028] Through a method according to the invention, the stabilized lignin can be obtained with a defined granulometric distribution. In this case, the separation of lignin from the lignin-containing liquid is greatly simplified compared to the prior art. For example, the granulometric distribution and polarity of the stabilized lignin are adjusted in such a way that the stabilized lignin can be separated from the liquid containing the stabilized lignin through filtration or decantation. Furthermore, on the basis of the method according to the invention it is possible to simplify the cleaning of lignin from inorganic components as well as compared to the state of the art.
    [029] According to the state of the art an acid acts catalytically on a hydrothermal carbonization of biomass. Furthermore, according to the state of the art, in the case of hydrothermal carbonization of biomass, acid is released in the form of mainly acetic acid, formic acid and levulinic acid. A hydrothermal carbonization of biomass is therefore done autocatalytically. According to the state of the art in a hydrothermal carbonization of lignin mainly few phenolic compounds are dissolved from it, the solid substance, however, remains preserved as such.
    [030] Surprisingly in the tests it was found that lignin during hydrothermal carbonization is polymerized with consumption of H+ ions. If few H+ ions are present in the lignin-containing liquid then lignin polymerization can be delayed or completely suppressed. If H+ ions are present in the lignin-containing liquid, then polymerization takes place. This measure takes advantage of the solution according to the invention.
    [031] An embodiment of a method according to the invention therefore differs from the known state of the art, in which acids are used as catalysts in order to reduce, for example, the reaction temperature of a hydrothermal carbonization, because in the method according to the invention acid is used merely to increase the ionic concentration of H+, and the H+ ions enable the polymerization of lignin in hydrothermal carbonization and are consumed in this case. The acid is used not as a catalyst, but as a participant in the reaction. This can be verified, for example, by the fact that during the adjustment of an ionic concentration of H+ in the liquid containing lignin before the hydrothermal carbonization that favors a polymerization of lignin, the ionic concentration of H+ is reduced after the hydrothermal carbonization, and the ions H+ were then consumed.
    [032] Also differently from the state of the art, it can be predicted that a base is used to reduce the ionic concentration of H+ and the polymerization of lignin is suppressed due to the lack of H+ ions. The base is used not as a catalyst, but for the binding of H+ ions. This can be verified, for example, by the fact that in the case of adjusting an ionic concentration of H+ in the liquid containing lignin before hydrothermal carbonization, which suppresses a polymerization of lignin, the ionic concentration of H+ after hydrothermal carbonization does not basically change. . If the smallest possible particle size distribution of the carbonized lignin is obtained then the polymerization should be slowed down or suppressed. Therefore, a minimum H+ ionic concentration must be set. If the largest possible particle size distribution of the carbonized lignin is obtained, then it will be necessary to enable the polymerization of the lignin. Therefore, it will be necessary to adjust a high ionic concentration of H+.
    [033] A difference of the method according to the invention in relation to the state of the art, which comprises the adjustment of the granulometric distribution of lignin in a precipitation process by adapting, for example, the pH value, the residence time and of the ionic strength, is that the particle size distribution of carbonized lignin is not obtained by adjusting the particle size distribution of lignin in a precipitation process before hydrothermal carbonization but that the ionic concentration of H+ is used before and/or during hydrothermal carbonization for the adjustment of the granulometric distribution of carbonized lignin. The particle size distribution of the carbonized lignin is preserved or as required by the method according to the invention in relation to the particle size distribution of a precipitated lignin according to the state of the art. Therefore, the granulometric distribution of a lignin precipitated according to the state of the art during its transfer to carbonized lignin using the method according to the invention can also be selectively maintained.
    [034] Preferably, the duration of the hydrothermal carbonization is at least one hour and at most 6 hours, especially preferably the duration is at least 2 hours and at most 4 hours. In one variant the duration of hydrothermal carbonization is approximately 3 hours.
    [035] In a variant of embodiment the duration of the hydrothermal carbonization is selected in such a way that a carbonized lignin with the desired granulometric distribution can be separated from the liquid containing carbonized lignin. In the case of such process conduction the duration of the hydrothermal carbonization can also be below one hour.
    [036] As illustrated above, acids are used, for example, for an increase in the ionic concentration of H+ and bases for a decrease in the ionic concentration of H+ in the lignin-containing liquid. For example, gases, which show with the lignin-containing liquid a basic reaction or an acid reaction, preferably CO2 or H2S for adjusting the ionic concentration of H+.
    [037] If, in addition to lignin, other organic polymers are present in the liquid containing lignin, for example, biomass, such as wood, straw, grass, etc., cellulose, hemicellulose and/or their degradation products, for example, glucose, etc., then from these organic polymers and their degradation products will be formed during hydrothermal carbonization organic acids, which increase the ionic concentration of H+ in the liquid containing lignin. In this context, it can be foreseen that in a variant of embodiment, the increase in the ionic concentration of H+ in the liquid containing lignin, which is due to the formation of organic acids during hydrothermal carbonization, is considered when adjusting the ionic concentration of H+ before and /or during hydrothermal carbonization. Alternatively or in addition, the ionic concentration of H+ can be increased during hydrothermal carbonization by increasing the percentage of biomass such as wood, straw, grass, cellulose, hemicellulose and/or their degradation products in the lignin-containing liquid before and/or during carbonization. hydrothermal.
    [038] In a variant of embodiment, the particle size distribution of carbonized lignin is measured continuously or regularly and, in case of deviation of the particle size distribution beyond a defined tolerance value, an adaptation of the ionic concentration of H+ in the liquid containing lignin is made. . Thus, for example, in the case of a necessary reduction in the particle size distribution of the carbonized lignin, the ionic concentration of H+ in the lignin-containing liquid is reduced before and/or during the hydrothermal carbonization and, in the case of a necessary increase in the particle size distribution of the carbonized lignin, the ionic concentration of H+ in the lignin-containing liquid increases before and/or during hydrothermal carbonization.
    [039] In a variant, the ionic concentration of H+ of the liquid containing carbonized lignin is measured after hydrothermal carbonization and used as a measure for the granulometric distribution. Preferably, the H+ ionic concentration of the carbonized lignin-containing liquid is adjusted after hydrothermal carbonization, and therefore, the grain size of the carbonized lignin is adjusted by adapting the H+ ionic concentration in the lignin-containing liquid before and/or during hydrothermal carbonization.
    [040] As a measure for the ionic concentration of H+ in the liquid containing lignin, the pH value can be used. Correspondingly in one variant the particle size distribution of the carbonized lignin can be adjusted by adapting the pH value of the lignin-containing liquid before and/or during hydrothermal carbonization. Preferably the pH value of the liquid containing the carbonized lignin is adjusted after the hydrothermal carbonization and therefore the grain size of the carbonized lignin by adapting the pH value of the liquid containing the lignin before and/or during the hydrothermal carbonization.
    [041] The aforementioned variants of a method according to the invention can also be combined with each other. POSSIBLE FORMS OF EMBODIMENT FOR CARGO MATERIALS
    [042] Possible embodiments of the method according to the invention will be presented below, which can be combined respectively with the aforementioned variants.
    [043] An embodiment of the method according to the invention is characterized, for example, by the fact that
    [044] - lignin is precipitated from the liquid containing lignin,
    [045] - the lignin-containing liquid is subjected under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C to 250°C, to a hydrothermal carbonization, in which the lignin is converted in a carbonized lignin,
    [046] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization and
    [047] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [048] In this embodiment of the method according to the invention the lignin, which is present first dissolved in the lignin-containing liquid, is precipitated and led to hydrothermal carbonization. For example, in the case of the lignin-containing liquid this is residual lye from a basic fractionation method, for example from a Kraft pulping process. This embodiment of the method according to the invention also contains a precipitation step prior to hydrothermal carbonization in which the pH value of the lignin-containing liquid is reduced such that lignin precipitates therefrom, preferably to a value between 9.5 and 10.5. For reducing the pH value acids or gases, which show an acidic reaction with the lignin-containing liquid, can be used. Preferably CO2 is used for the reduction of the pH value. Preferably, in this embodiment of the method according to the invention, a colloidal lignin or a fine sediment of carbonized lignin is obtained.
    [049] Another embodiment of the method according to the invention is characterized for example by the fact that
    [050] - lignin is precipitated from a first liquid containing lignin,
    [051] - the precipitated lignin is separated from the first lignin-containing liquid,
    [052] - the precipitated and separated lignin is suspended in a liquid and thus a second lignin-containing liquid is obtained, whereby the precipitated and separated lignin in an improvement can also be dissolved in the liquid at least partially or totally,
    [053] - the second liquid containing lignin under temperatures in a range of approximately 150°C to approximately 280°C, preferably between 200°C and 250°C, be subjected to a hydrothermal carbonization, in which the lignin is converted into a carbonized lignin,
    [054] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization and
    [055] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [056] In this embodiment of the method according to the invention the lignin, which is present first dissolved in a first lignin-containing liquid, is precipitated and then largely separated from that first lignin-containing liquid. The lignin precipitated in large part from the first lignin-containing liquid is suspended in a liquid and if necessary dissolved in which a second lignin-containing liquid is obtained, which is then led to hydrothermal carbonization. For example, in the case of the first lignin-containing liquid it is residual lye from a basic fractionation process, for example a Kraft pulping process. This embodiment of the method according to the invention also includes a precipitation step and a separation step before hydrothermal carbonization.
    [057] In the precipitation step the pH value of the lignin-containing liquid is reduced such that the lignin precipitates from it, preferably to a value between 9.5 and 10.5. Acids or gases can be used to reduce the pH value which show an acidic reaction with the lignin-containing liquid. Preferably CO2 is used for lowering the pH value.
    [058] In the separation step, the first liquid containing lignin is separated as much as possible from the precipitated lignin. For the separation step, a filter press, a membrane filter press or a decanter can be used. During the separation step, inorganic impurities of the lignin are also preferably separated with the lignin-containing liquid. The liquid containing lignin - after the precipitated lignin has been separated from it - has a very low lignin content. In this preferred embodiment of the method according to the invention, a fine sediment of carbonized lignin is obtained.
    [059] A first embodiment of the method according to the invention is characterized by the fact that
    [060] - the lignin will be dissolved in the liquid containing lignin,
    [061] - the lignin-containing liquid under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C to 250°C, is subjected to a hydrothermal carbonization in which the lignin is converted into a carbonized lignin,
    [062] - lignin during its conversion to carbonized lignin during hydrothermal carbonization precipitates or is partially precipitated from the lignin-containing liquid,
    [063] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the lignin-containing liquid before or during hydrothermal carbonization,
    [064] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [065] In this embodiment of the method according to the invention the lignin is dissolved before hydrothermal carbonization in the lignin-containing liquid. For example, in the case of lignin-containing liquid this is residual lye resulting from the basic fractionation process, for example from a Kraft pulping process. Lignin, which is not dissolved in the lignin-containing liquid, can be brought into solution by first increasing the pH value and then conducted as dissolved lignin to hydrothermal carbonization. The dissolved lignin is precipitated in this embodiment at least partially during hydrothermal carbonization. After the hydrothermal carbonization, a further precipitation of the carbonized lignin still dissolved in the liquid containing carbonized lignin can be carried out. Preferably, in this embodiment of the method according to the invention, a colloidal lignin or a fine sediment of carbonized lignin is obtained. POSSIBLE FORMS OF CONFIRMATION FOR PRODUCTS
    [066] Three alternative embodiments of the method according to the invention will be presented by way of example.
    [067] Thus, a method can be envisaged for obtaining carbonized lignin with a defined granulometric distribution resulting from a liquid containing lignin, in which
    [068] - the liquid containing lignin under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C to 250°C is subjected to a hydrothermal carbonization, in which the lignin is converted into a carbonized lignin,
    [069] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the liquid containing lignin before and/or during hydrothermal carbonization in such a way that a colloidal carbonized lignin is formed, and the pH value of the liquid containing lignin before and during hydrothermal carbonization does not exceed a value of 10, and
    [070] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [071] In this embodiment variant it is possible by adjusting the ionic concentration of H+ in the liquid containing lignin that a colloidal carbonized lignin is formed. In this case, an ionic concentration of H+ is foreseen before and during hydrothermal carbonization, which corresponds to a pH value of >= 10. By adjusting the ionic concentration of H+, it is possible to suppress a polymerization of lignin during hydrothermal carbonization. Furthermore, it is possible that the particle size distribution and functional groups of the carbonized lignin are applied in such a way that a colloidal carbonized lignin is formed. Preferably the carbonized colloidal lignin is separated by filtration at a temperature of preferably at least 60°C from the liquid containing the carbonized colloidal lignin.
    [072] In another variant, a method is provided in which
    [073] - the lignin-containing liquid under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C to 250°C, is subjected to a hydrothermal carbonization, in which the lignin is converted in a carbonized lignin,
    [074] - the granulometric distribution of carbonized lignin by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization is adjusted in such a way that a fine sediment of carbonized lignin is formed, and
    [075] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [076] Preferably the pH value of the lignin-containing liquid before hydrothermal carbonization is >7, especially preferably >8, and during hydrothermal carbonization is between 7 and 11, especially preferably between 8 and 10.
    [077] In this embodiment variant it is possible by adjusting the ionic concentration of H+ in the liquid containing lignin that a fine sediment of carbonized lignin is formed. In this case, an ionic concentration of H+ corresponding to a pH value > 7 is preferably provided before the hydrothermal carbonization. During the hydrothermal carbonization, an ionic concentration of H+ corresponding to a pH value between 7 and 11 is preferably provided. adjustment of the ionic concentration of H+ it is possible that the formation of coarse particles is largely suppressed through a polymerization of lignin during hydrothermal carbonization. Furthermore, it is possible that the particle size distribution and functional groups of the carbonized lignin are applied in such a way that a fine sediment of carbonized lignin is formed.
    [078] In another variant, a method is provided for obtaining carbonized lignin with defined granulometric distribution from a liquid containing lignin, in which
    [079] - the lignin-containing liquid under temperatures in a range of approximately 150°C to approximately 280°C, preferably in a range of 200°C to 250°C, is subjected to a hydrothermal carbonization, in which the lignin is converted in a carbonized lignin,
    [080] - the granulometric distribution of carbonized lignin is adjusted by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization in such a way that a thick sediment of carbonized lignin is formed, and
    [081] - the carbonized lignin is separated from the liquid containing the carbonized lignin.
    [082] Preferably in this case the pH value of the lignin-containing liquid before hydrothermal carbonization is < 9, especially preferably < 8, and during hydrothermal carbonization < 8.
    [083] In this embodiment variant it is possible by adjusting the ionic concentration of H+ in the liquid containing lignin that a thick sediment of carbonized lignin is formed. In this case, an ionic concentration of H+ corresponding to a pH value < 9 is preferably provided before hydrothermal carbonization. During hydrothermal carbonization, an ionic concentration of H+ corresponding to a pH value < 8 is preferably provided. ionic concentration of H+ it is possible that the formation of coarse particles is favored by a polymerization of lignin during hydrothermal carbonization. Furthermore, it is possible that the particle size distribution and functional groups of the carbonized lignin are applied in such a way that a thick sediment of carbonized lignin is formed. SPECIFIC ACHIEVEMENT EXAMPLES
    [084] Other examples of implementation will be explained below, which can be seen in more detail in the attached figures 1 to 4. Example of embodiment 1 (fig 1)
    [085] In the example of embodiment 1, a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution on black liquor resulting from an alkaline fractionation process according to the Kraft method. Through the method a fine sediment of carbonized lignin is produced. The example of embodiment is illustrated in figure 1.
    [086] Black liquor (1.1) is taken from the Kraft process evaporation plant with a dry substance content of approximately 30 Ma. -% and represents the liquid containing lignin. The pH value of black liquor is approximately 13. Lignin is dissolved in the black liquor.
    [087] Firstly, the pH value of black liquor is reduced by introducing CO2 (6.1) into a device for reducing pH (A.1) to approximately 10.5. The previously treated black liquor (2.1) is hydrothermally carbonized for a period of 3 hours and at a temperature of 250°C in a hydrothermal carbonization (B.1).
    [088] During hydrothermal carbonization the carbonized lignin precipitates from the black liquor. Based on the process conduction before hydrothermal carbonization in the device for reducing pH (A.1) it can also precipitate lignin from black liquor. The preponderant part, however, precipitates during hydrothermal carbonization. The pH value of carbonized black liquor (3.1) is, after hydrothermal carbonization, approximately 9.5. The precipitated carbonized lignin is separated from the carbonized black liquor through mechanical drainage (C.1) in a filter press and a filter cake is obtained. The filtrate thus obtained (5.1) is returned to the evaporation plant of the Kraft process. Then the filter cake is washed with water (7.1). After washing (8.1) the washing water is returned to the Kraft process evaporation plant. The desired filter cake (4.1) is composed of a fine sediment of carbonized lignin and remaining water and is carried out of the process.
    [089] To determine the Q3 distribution of the grain size of the fine carbonized lignin sediment, the filter cake (4.1) was diluted with distilled water, with the aid of ultrasound dispersed for a period of 120 seconds measured by laser diffraction with the laser granulometer device Cilas 1190. The granulometric distribution thus obtained of the fine carbonized lignin sediment is illustrated in figure 5, which shows the Q3 distribution of the carbonized lignin for the example of embodiment 1. The D90 is 334.87 μm and the D50 is 47.93 μm. Example of embodiment 2 (fig 2)
    [090] In the example of embodiment 2 a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution on black liquor resulting from an alkaline fractionation process according to the Kraft method. Through the method a colloidal carbonized lignin is produced. The example of embodiment is illustrated in figure 2.
    [091] Black liquor (1.2) is taken from the Kraft process evaporation plant with a dry substance content of 30 Ma. -% and represents the liquid containing lignin. The pH value of black liquor is approximately 13. The lignin is dissolved in the black liquor.
    [092] First, the pH value of black liquor is reduced by introducing CO2 (6.2) into a device for reducing pH (A.2) to approximately 11.5. The previously treated black liquor (2.2) is hydrothermally carbonized for a period of 3 hours and at a temperature of 250°C in a hydrothermal carbonization (B.2). During hydrothermal carbonization the carbonized lignin precipitates from the black liquor. The pH value of carbonized black liquor (3.2) is, after hydrothermal carbonization, approximately 10.5. The precipitated carbonized lignin is separated from the carbonized black liquor through a mechanical drainage (C.2) at a temperature of 80°C by filtration. The filtrate thus obtained (5.2) is returned to the evaporation plant of the Kraft process. The filter cake (4.2) is composed of a carbonized lignin, colloidal and remaining carbonized black liquor and is transported out of the process.
    [093] To determine the Q3 grain size distribution of carbonized lignin, the colloidal filter cake (4.2) was diluted with distilled water, with the aid of ultrasound for a period of 30 seconds, dispersed and measured by laser diffraction with the laser granulometer device Cilas 1190. The granulometric distribution of the colloidal carbonized lignin in this way is illustrated in figure 6, which shows the Q3 distribution of the carbonized lignin for the example of embodiment 2. The D90 is 11.96 μm and the D50 is 4.2 μm. Example of embodiment 3a (fig 3)
    [094] In the example of embodiment 3a, a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution in colloidal lignin. The lignin content of colloidal lignin is above 90%.
    [095] Colloidal lignin is precipitated by acidification of black liquor (1.3) with CO2, (6.3) in a device for reducing the pH value (A.3) which is taken from the evaporation plant of a Kraft process, from the said black liquor. Then the mixture of black liquor and precipitated lignin (2.3) is returned to a filtering membrane press (D.3) and mechanically drained. The filtrate from the membrane filter press (10.3) is fed back to the evaporation plant of the Kraft process. The pH value of the thus obtained filter cake of colloidal lignin (9.3) is situated at approximately 9, the dry substance content at approximately 55%. Using the method according to the invention, a fine sediment of carbonized lignin is then produced from the colloidal lignin contained in the filter cake.
    [096] The colloidal lignin filter cake (9.3) is first diluted in a device for mixing (E.3) with water at a dry substance content of approximately 20%, in which the lignin-containing liquid is obtained. The pH value of the lignin-containing liquid is reduced by adding H2SO4 (12.3) in the mixing device (E.3) to approximately 8. The thus treated lignin-containing liquid (11.3) is hydrothermally carbonized for a period of 3 hours and at a temperature of 230°C in a hydrothermal carbonization (B.3). The pH value of the liquid containing the carbonized lignin (3.3) is, after hydrothermal carbonization, approximately 8.
    [097] The carbonized lignin is separated from the liquid containing the carbonized lignin through a mechanical drainage in a membrane filter press (C.3), in which a filter cake is obtained. The filtrate thus obtained (5.3) is fed back to the evaporation plant of the Kraft process. Then the filter cake is washed with water (7.3). The wash water in this case (8.3) is used for the dilution of the colloidal lignin filter cake to a dry substance content of approximately 20% before hydrothermal carbonization. The washed filter cake (4.3) is composed of a fine sediment of carbonized lignin and remaining water and is transported out of the process.
    [098] To determine the Q3 distribution of the grain size of the fine carbonized lignin sediment, the filter cake (4.3) was diluted with distilled water, with the aid of ultrasound for a period of 120 seconds, dispersed and measured by laser diffraction with the laser granulometry apparatus Cilas 1190. The granulometric distribution thus measured of the fine sediment of carbonized lignin is shown in Figure 7, which shows the Q3 distribution of carbonized lignin for the example of embodiment 3a. The D90 is 197.91 μm and the D50 is 29.24 μm. Example of embodiment 3b (fig 3)
    [099] In the example of embodiment 3b, a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution in colloidal lignin. The lignin content of colloidal lignin is above 90%.
    [0100] Colloidal lignin by acidification of black liquor (1.3) with CO2, (6.3) in a device for reducing the pH value (A.3) which is taken from the evaporation plant of a Kraft process, is precipitated from the said black liquor. Then, the mixture of black liquor and precipitated lignin (2.3) is returned to a membrane filter press (D.3) and mechanically drained there. The filtrate from the membrane filter press (10.3) is fed back to the evaporation plant of the Kraft process. The pH value of the thus obtained filter cake of colloidal lignin (9.3) is situated at approximately 9, the dry substance content at approximately 55%. Using the method according to the invention, a fine sediment of carbonized lignin is then produced from the colloidal lignin contained in the filter cake.
    [0101] The colloidal lignin filter cake (9.3) is first diluted in a device for mixing (E.3) with water at a dry substance content of approximately 20%, in which the lignin-containing liquid is obtained. The pH value of the lignin-containing liquid is changed in embodiment example 3b, unlike embodiment example 3a not by adding H2SO4. Stream 12.3 is therefore zero. The lignin-containing liquid thus treated (11.3) is hydrothermally carbonized for a period of 3 hours and at a temperature of 230°C in a hydrothermal carbonization (B.3). The pH value of the liquid containing the carbonized lignin (3.3) is, after hydrothermal carbonization, approximately 8.5.
    [0102] The carbonized lignin is separated from the liquid containing the carbonized lignin through a mechanical drainage in a membrane filter press (C.3) and a filter cake is obtained. The filtrate thus obtained (5.3) is returned to the evaporation plant of the Kraft process. Then the filter cake is washed with water (7.3). The washing water (8.3) in this incident case is used to dilute the colloidal lignin filter cake to a dry substance content of approximately 20% before hydrothermal carbonization. The washed filter cake (4.3) is composed of a fine sediment of carbonized lignin and remaining water and is transported out of the process.
    [0103] To determine the Q3 distribution of the grain size of the fine carbonized lignin sediment, the filter cake (4.3) was diluted with distilled water, with the aid of ultrasound for a period of 120 seconds, dispersed and measured by laser diffraction with the laser granulometer apparatus Cilas 1190. The granulometric distribution thus obtained of the fine carbonized lignin sediment is illustrated in figure 8, which shows the Q3 Distribution of the carbonized lignin for the example of embodiment 3b. The D90 is 13.88 μm and the D50 is 4.62 μm.
    [0104] The comparison of embodiment example 3a and 3b shows how through an increase in the ionic concentration of H+ by the additional addition of H2SO4 after the addition of CO2 in example 3a, one can interfere in the granulometric distribution of carbonized lignin and in relation to to example embodiment 3b to obtain a thicker product. Example of embodiment 4a (fig 4)
    [0105] In the example of embodiment 4a, a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution in a filter cake containing lignin resulting from the hydrolysis process. The lignin content of the filter cake is approximately 70%. Using the method, a fine sediment of carbonized lignin is produced from lignin.
    [0106] The lignin-containing filter cake (9.2) is first diluted in a device for mixing (E.4) with water at a dry substance content of approximately 20% in which the lignin-containing liquid is obtained. The pH value of the lignin-containing liquid is approximately 4.5. Then the pH value is increased by adding KOH (12.4) to approximately 10. The liquid containing lignin thus treated (11.4) is hydrothermally carbonized for a period of 3 hours and at a temperature of 250°C in a hydrothermal carbonization ( B.4). The pH value of the liquid containing the carbonized lignin (3.4) is, after hydrothermal carbonization, approximately 5. The carbonized lignin is separated from the liquid containing the carbonized lignin through a mechanical drainage (C.4) in a filter press of membrane.
    [0107] The filtrate in this incident case (8.4) is partially used for diluting the filter cake to a dry substance content of approximately 20% before hydrothermal carbonization in E.4 and transported partially out (5.4) of the process. The filter cake (4.4) is composed of a fine sediment of carbonized lignin and the remaining liquid is carried out of the process.
    [0108] To determine the Q3 distribution of the grain size of the fine carbonized lignin sediment, the filter cake (4.4) was diluted with distilled water, with the aid of ultrasound for a period of 60 seconds, dispersed and measured by laser diffraction with the laser granulometer apparatus Cilas 1190. The granulometric distribution thus determined of the fine carbonized lignin sediment is illustrated in figure 9, which shows the Q3 distribution of the carbonized lignin for the example of embodiment 4a. The D90 is 46.69 μm and the D50 is 15.20 μm. Example of embodiment 4b (fig 4)
    [0109] In the example of embodiment 4b, a method according to the invention is applied to obtain a stabilized lignin with defined granulometric distribution in a filter cake containing lignin resulting from the hydrolysis process. The lignin content of the filter cake is approximately 70%. Using the method, a fine sediment of carbonized lignin is produced from lignin.
    [0110] The filter cake containing lignin (9.2) is first in a device for mixing (E.4) diluted with water in a dry substance content of approximately 15%, being obtained the liquid containing lignin. The pH value of the lignin-containing liquid is approximately 5. The pH value of the lignin-containing liquid is changed differently from embodiment example 4a not by adding KOH. Stream 12.4 is therefore zero. The lignin-containing liquid (11.4) is hydrothermally carbonized for a period of 3 hours and at a temperature of 230°C in a hydrothermal carbonization (B.4). The pH value of the liquid containing the carbonized lignin (3.4) is approximately 4 after hydrothermal carbonization. The carbonized lignin is separated from the liquid containing the carbonized lignin by mechanical drainage (C.4) in a membrane filter press. The filtrate formed in this case is partially (8.4) used for diluting the filter cake to a dry substance content of approximately 15% before hydrothermal carbonization in E.4 and transported partially out (5.4) of the process. The filter cake (4.4) is composed of a fine sediment of carbonized lignin and remaining liquid and is discharged from the process.
    [0111] To determine the Q3 distribution of the grain size of the fine carbonized lignin sediment, the filter cake (4.4) was diluted with distilled water, with the aid of ultrasound for a period of 60 seconds, dispersed and measured by laser diffraction with the laser granulometer apparatus Cilas 1190. The granulometric distribution thus determined of the fine sediment of carbonized lignin is shown in figure 10, which shows the Q3 Distribution of carbonized lignin for the example of embodiment 4b. The D90 is 77.98 μm and the D50 is 32.33 μm.
    [0112] The comparison of embodiment examples 4a and 4b shows how, by decreasing the ionic concentration of H+ by the addition of KOH in example 4a, one can interfere in the granulometric distribution of carbonized lignin and obtain a finer product in relation to the embodiment example 4b.
    权利要求:
    Claims (15)
    [0001]
    1. PROCESS FOR RECOVERING CARBONIZED LIGNIN, with defined granulometric distribution from a liquid containing lignin, in which the liquid containing lignin is subjected to hydrothermal carbonization to convert the lignin into carbonized lignin and the carbonized lignin is separated from the liquid containing the carbonized lignin, characterized in that - the liquid containing lignin is subjected to hydrothermal carbonization at temperatures in the range of 150 °C to 280 °C and - by adapting the ionic concentration of H+ in the liquid containing lignin before and/or before and during carbonization hydrothermal the particle size distribution of the carbonized lignin is adjusted, - in which a low ionic concentration of H+ is adjusted to obtain the smallest possible particle size distribution of the carbonized lignin, and - a high ionic concentration of H+ is adjusted to obtain the largest possible particle size distribution of the carbonized lignin.
    [0002]
    2. PROCESS, according to claim 1, characterized in that the liquid containing lignin is subjected to hydrothermal carbonization at temperatures in the range of 200 °C to 250 °C.
    [0003]
    Process according to any one of claims 1 or 2, characterized in that the lignin-containing liquid is subjected to hydrothermal carbonization for a period of at least 1 hour and at most 6 hours.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that - by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization, the granulometric distribution of the carbonized lignin is adjusted so that the carbonized lignin colloidal is formed either - by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization the particle size distribution of the carbonized lignin is adjusted so that a fine sediment of carbonized lignin is formed or - by adapting the ionic concentration of H+ in the lignin-containing liquid before and/or during hydrothermal carbonization the particle size distribution of the carbonized lignin is adjusted so that a thick sediment of carbonized lignin is formed.
    [0005]
    Process according to claim 4, characterized in that - for the formation of colloidal carbonized lignin, the ionic concentration H+ is adapted in such a way that the pH value of the lignin-containing liquid before and during hydrothermal carbonization does not fall below a value of 10, - for the formation of a fine sediment of carbonized lignin, the ionic concentration H+ is adapted such that the pH value of the lignin-containing liquid before and during hydrothermal carbonization is > 7, or - for formation of a thick sediment of carbonized lignin, the H+ ion concentration should be adapted such that the pH value of the lignin-containing liquid before and during hydrothermal carbonization is < 9.
    [0006]
    Process according to claim 5, characterized in that - for the formation of a fine sediment of carbonized lignin, the ionic concentration H+ is adapted in such a way that the pH value of the liquid containing lignin before hydrothermal carbonization is > 7 and, during hydrothermal carbonization, between 7 and 11 or - for the formation of a thick sediment of carbonized lignin, the ionic concentration H+ is adapted in such a way that the pH value of the liquid containing lignin before hydrothermal carbonization is < 9, in particular, < 8 and, during hydrothermal carbonization, be < 8.
    [0007]
    Process according to claim 6, characterized in that, for the formation of a fine sediment of carbonized lignin, the ionic concentration H+ is adapted in such a way that the pH value of the liquid containing lignin before the hydrothermal carbonization is > 8 and/or, during hydrothermal carbonization is between 8 and 10.
    [0008]
    Process according to any one of claims 5 to 7, characterized in that, for the formation of a fine sediment of carbonized lignin, the ionic concentration H+ is adapted in such a way that the D90 of the fine sediment of carbonized lignin is < 100 μm or < 100 μm.
    [0009]
    A process according to any one of the preceding claims, characterized in that the lignin is dissolved in the lignin-containing liquid before hydrothermal carbonization to a greater extent than 50%, especially above 60% or above 70%.
    [0010]
    10. PROCESS, according to any one of the preceding claims, characterized in that, to increase the ionic concentration H+ in the liquid containing lignin, an acid is used, which is a participant in the reaction during hydrothermal carbonization, or to reduce the ionic concentration H+ in the lignin-containing liquid, a base that binds to H+ ions is used.
    [0011]
    11. PROCESS, according to any one of the preceding claims, characterized in that CO2 or H2S is used to adapt the ionic concentration of H+.
    [0012]
    Process according to any one of the preceding claims, characterized in that the method is applied in - black liquor resulting from an alkaline fractionation process, especially according to the KRAFT process or - a liquid containing lignin recovered by diluting a cake of filtration containing lignin, especially by diluting a filter cake containing a black liquor lignin precipitate or by diluting a filter cake from the residue containing lignin residue resulting from a hydrolysis.
    [0013]
    Process according to any one of the preceding claims, characterized in that - the lignin is precipitated from a first lignin-containing liquid, - the precipitated lignin is separated from the first lignin-containing liquid, - the precipitated and separated lignin is suspended in a liquid and thus a second lignin-containing liquid is obtained and - the second lignin-containing liquid is subjected to hydrothermal carbonization.
    [0014]
    Process according to any one of the preceding claims, characterized in that the lignin precipitate is precipitated from the lignin-containing liquid, at least partially upon conversion to carbonized lignin during hydrothermal carbonization.
    [0015]
    Process according to any one of the preceding claims, characterized in that carbonized lignin is separated from the liquid containing carbonized lignin through mechanical drainage and the separated lignin is washed.
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    同族专利:
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    WO2016020383A1|2016-02-11|
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    DE102014215807B3|2015-12-24|
    US10415184B2|2019-09-17|
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    CN106574053A|2017-04-19|
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    CA2957461A1|2016-02-11|
    EP3177767B1|2020-04-08|
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    CN106574053B|2020-06-02|
    PL3177767T3|2020-10-19|
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    法律状态:
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-02-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/08/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    DE102014215807.9A|DE102014215807B3|2014-08-08|2014-08-08|Process for obtaining a stabilized lignin with a defined grain size distribution from a lignin-containing liquid|
    DE102014215807.9|2014-08-08|
    PCT/EP2015/067958|WO2016020383A1|2014-08-08|2015-08-04|Method for obtaining stabilized lignin having a defined particle-size distribution from a lignin-containing liquid|
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