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    • 专利摘要:
    Lignocellulosic biomass depolymerization method. This document describes a depolymerization method from lignocellulosic biomass that comprises operating in a liquid medium that acts as a solvent, at a process temperature below 200ºC, and at atmospheric pressure, under conditions that allow the distillation of volatile compounds from the medium. solvent and, preferably, isolation of the furfural comprised in the distillate by condensation. This method also comprises the separation of the solid (mostly cellulose) present in the solvent medium enriched in derivatives of the depolymerization of lignin obtained after the depolymerization reaction. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2819834A1
    申请号:ES201930919
    申请日:2019-10-17
    公开日:2021-04-19
    发明作者:Gil Jesus Martin；Juan Celia Andres；Duran Laura Buzon；Lebena Eduardo Perez；Ramos Pablo Martin
    申请人:Universidad de Valladolid；
    IPC主号:
    专利说明:

    [0004] TECHNICAL SECTOR
    [0006] The present invention is framed in the fields of Chemistry and Engineering, and has a direct application in the agricultural-forestry sector, since it promotes the use of lignocellulosic biomass to obtain products with an improved surplus value compared to the material. original cousin. More specifically, it provides a depolymerization method from lignocellulosic biomass that makes it possible to obtain the fundamental components of this biomass (in particular, cellulose) or its depolymerization derivatives (in particular, derivatives of lignin and hemicellulose) in separate fractions. , which can be valued independently of each other.
    [0008] Thus, in the depolymerization method from lignocellulosic biomass described here, a solid fraction comprising cellulose is obtained, a liquid fraction comprising compounds derived from the depolymerization of lignin (in particular, phenolic compounds) and, preferably, a gaseous fraction comprising dehydration products of hemicellulose (water and furfural). In this way, the method of the present invention allows the separate use of the different fundamental components of lignocellulosic biomass (cellulose, hemicellulose and lignin).
    [0010] This depolymerization method is characterized by working under mild conditions, with a temperature lower than 200 ° C and at atmospheric pressure, which allows to extend the life of the equipment used to carry out the method, as it is not severely mechanically stressed.
    [0012] STATE OF THE ART
    [0014] Biomass in general and its possible treatments are an old aspiration of Chemical Engineering, which has developed numerous processes and facilities for this purpose. At this time, and protected by government and EU interest, there is growing interest in biomass as an energy source, since its use or that of its derivatives can be considered neutral in terms of net CO2 emissions. The adverse effects of The continued emission of greenhouse gases and the current climate change have promoted a growing search for new methods to process biomass and obtain alternative biofuels. The use of agricultural and forestry residues and lignocellulosic biomass in general can contribute to alleviate the problems associated with climate change, which are increasingly pressing and currently rigorous.
    [0016] Among the traditional methods developed to process lignocellulosic biomass, pyrolysis and gasification stand out. The main problem of the gasification technique is that the biomass is highly oxygenated and is deficient in hydrogen, so this must be added for the correct elaboration of the hydrocarbons, which entails a high cost. In addition, despite the fact that the use of gasification to obtain a lean gas, to be used as fuel in cogeneration engines, has been extensively investigated, the units that have been implemented have always suffered innumerable problems, and at this time there is no technology reliable implanted in the market.
    [0018] On the other hand, pyrolysis (in particular, flash pyrolysis) is an alternative process where the biomass is treated in the absence of oxygen, at temperatures of 400 ° C to 750 ° C, with a very high heating rate (from one thousand to ten thousand degrees per second), followed by rapid condensation of the vapors. The main products of the pyrolysis process are carbon (biochar) and bio-oils (up to 80% yield). These bio-oils are dark brown, corrosive, smoky-smelling liquids, made up of polar organic compounds (75-80% by weight) and water (approx. 20% to 25% by weight). The chemical composition of bio-oils is very complex, made up of a mixture of more than 400 highly oxygenated compounds, including carboxylic acids, alcohols, aldehydes, esters, ketones and aromatic species, together with some polymeric carbohydrates and lignin fragments. Bio-oils retain up to 70% of the energy stored in biomass (16 MJ / Kg-1) but present numerous drawbacks for their direct use as fuels. These include its high acidity (pH = 2-3), high viscosity (cP 35-1000 at 40 ° C), and low chemical stability. Consequently, the greatest technological challenge of this technology is to develop efficient routes to refine bio-oils and transform them into high-performance biofuels. For this, different catalytic routes are currently being investigated (for example, EP0904335 B1, EP0670873 B1, EP0221679 B1) aimed at reducing their oxygen content and increasing their calorific value and stability.
    [0019] The transformation of sugars present in biomass into bioethanol has also been described (WO07 / 082976 A1; WO2010 / 006840 A2). Cellulose and hemicellulose are polymers of sugars, which depolymerized can be fermented to ethanol. Among the main drawbacks of this procedure, we must point out that the lignin fraction (its percentage is 27-30% in many forest species) remains as a residue in the process and, therefore, is not used.
    [0021] One of the inventors of this patent application filed and obtained two Spanish patents related to the complete transformation of lignocellulosic biomass: P201230430, filed on March 22, 2012 (published as ES2412241 A1); and P201330874, of June 12, 2013 (published as ES2415030 A1). Both methods describe biomass liquefaction methods within an aqueous solvent, at pressures above atmospheric. In the processes described in these patents, the total transformation of the three components of lignocellulosic biomass is obtained: lignin, hemicellulose and cellulose. In contrast to these processes, the present invention provides an improved method that allows the fundamental components of lignocellulose biomass to be harnessed separately. Thus, in the method described here, a solid fraction comprising cellulose, a liquid fraction comprising compounds derived from depolymerization of lignin (in particular phenolic compounds) and, preferably, a gaseous fraction comprising furfural, derived compound of the depolymerization and dehydration of hemicellulose.
    [0023] Patent application US2011144359A1 discloses a method that comprises a first stage of pre-treatment of lignocellulosic biomass, and a second stage where the production of furfural takes place from the hydrolyzed hemicellulose obtained in the previous stage. According to this method, the lignocellulosic material is put in contact with a mixture formed by water and an organic acid (specifically formic acid, acetic acid, citric acid or oxalic acid), preferably at a temperature between 130 ° C and 180 ° C and at a pressure that can be equal to or greater than atmospheric, provided that it is high enough so that the water does not boil at the reaction temperature (see paragraph [0038]). In this way, a first liquid phase is obtained that contains hydrolyzed hemicellulose and a second phase that comprises lignin and cellulose. These phases are separated and, by heating the first liquid phase, that is, the one containing the hydrolyzed hemicellulose (in particular xylose) at a temperature of at least 130 ° C, furfural is obtained. In this patent application it is also describes the separation of lignin and cellulose, by dissolving the former in a mixture of water and C1-C3 chain alcohol, preferably at a temperature of 50 ° C (see paragraph [0065]).
    [0025] In essence, by means of this method, furfural is obtained from lignocellulosic biomass, but the lignin is not depolymerized since it is not soluble in water and, therefore, does not dissolve in the reaction medium. On the other hand, taking into account that the boiling temperature of water at atmospheric pressure is 100 ° C, to maintain a reaction temperature higher than 130 ° C and prevent the water from boiling (as specifically indicated by US2011144359), it is necessary to work at a pressure higher than atmospheric. Consequently, in the method described in this American patent application, it is not possible to feed lignocellulosic biomass in semi-continuous, that is, without the need to carry out cumbersome cooling / heating and depressurization / pressurization processes of the system between different cycles. production, which is desirable and appropriate to optimize the efficiency of lignocellulosic biomass treatment.
    [0027] In the method described in this patent application organic solvents are used, in particular glycol ethers, levulinic acid or a combination of the above. The use of these organic solvents facilitates the dissolution and depolymerization of the lignin in the reaction medium.
    [0029] On the other hand, patent application CN108530404A shows a method for the treatment of lignocellulosic biomass and the production of furfural, cellulose and lignin. For this, the biomass is introduced into a reactor, mixed with water, acetone, phosphoric acid and sulfuric acid. The reactor works at a pressure of 0.5 to 2 MPa. As in patent application US2011144359A1, the method described here uses water as a solvent, so the lignin does not decompose or dissolve in the medium and, additionally, it does not allow the continuous feeding of the biomass, since it works at high pressures, from 5 to 20 bar.
    [0031] Finally, patent application WO2011149341A1 presents a method for treating lignocellulosic biomass, at a temperature of 75 ° C, in the presence of an ionic liquid and an organic acid. In this way a mixture comprising cellulose is produced as a result. Subsequently, the cellulose is precipitated. The fundamental drawback of this process is that ionic liquids are very expensive and therefore this method is not profitable.
    [0032] DESCRIPTION OF THE INVENTION
    [0034] An object of the present invention is a method of transformation of lignocellulosic biomass, by means of a depolymerization process, which comprises the following stages:
    [0035] a) obtaining a solvent medium comprising an acid catalyst, preferably para-toluenesulfonic acid, and a solvent selected from the group consisting of glycol ether, levulinic acid, and a combination of the foregoing;
    [0036] b) adjusting the temperature of the solvent medium of step a) between 150 ° C and 200 ° C, preferably between 165 ° C and 190 ° C;
    [0037] c) adding lignocellulosic biomass to the solvent medium of step b), maintaining stirring, atmospheric pressure and a temperature between 150 ° C and 200 ° C, preferably between 165 ° C and 190 ° C;
    [0038] d) maintaining the conditions established in step c) for a reaction period of at least 5 minutes, under conditions that allow the distillation of volatile compounds (in particular, water and furfural) from the solvent medium; Y
    [0039] e) solid-liquid separation of the solid (mostly cellulose) present in the enriched solvent medium obtained after step d), preferably by centrifugation, for example, in a decanter centrifuge connected to the reactor vessel where the biomass treatment takes place.
    [0041] In preferred embodiments of the present invention, steps b) to d) take place at a temperature between 165 ° C and 190 ° C, so that the furfural obtained by depolymerization and dehydration of the hemicellulose present in the lignocellulosic biomass evaporates from the medium. solvent by distillation. In these embodiments, the method described here comprises an additional step d-1) of condensation of the furfural comprised in the distillate of step d) by cooling, in particular at a temperature below 160 ° C, of this distillate.
    [0043] In this way, the method of the present invention allows the use of furfural, one of the products obtained by depolymerization of lignocellulosic biomass and, additionally, the problems that this compound can generate of remaining in the reaction medium due to its tendency to polymerize.
    [0044] The enriched solvent medium obtained after step e) is a liquid comprising the catalyst and solvent from step a) and, additionally, is enriched in derivatives of the depolymerization of lignin, in particular phenolic compounds. From the depolymerization of lignin, a great variety of phenolic compounds are obtained, mainly formed by units of phenylpropanic acids with different functional groups.
    [0046] In particular embodiments of the present invention, in the depolymerization method from lignocellulosic biomass described here, steps a) to e), including when applying the aforementioned furfural condensation step d-1), are repeated n times, n being a number greater than 1, and at least part of the enriched solvent medium obtained after the solid-liquid separation of stage e) of a cycle is used as solvent medium in stage a) of a subsequent cycle. The value of n is variable depending on the type of biomass and, in particular, on the lignin content present in the starting biomass. More specifically, the higher the lignin content in the biomass, the lower the n value, since the viscosity of the enriched solvent medium increases with each cycle, making the procedure more difficult. By way of example, if the lignocellulosic biomass is cereal straw, the value n can be greater than 20.
    [0048] In step c) of the method described here, the depolymerization process of the lignin present in the lignocellulosic biomass and the dissolution of the depolymerization products, in particular, phenolic compounds, in the solvent medium is started. Likewise, in this same reaction period, the depolymerization of the hemicellulose present in the biomass takes place, and the subsequent dehydration of the sugars obtained to furfural and water. When this step d) is carried out under conditions that allow the distillation of furfural from the reaction medium, preferably at a temperature between 165 ° C and 190 ° C, this compound can be isolated by condensation of the distillate, that is, by cooling the distillate to a temperature sufficient to achieve condensation of furfural, in particular at a temperature equal to or less than 160 ° C.
    [0050] The lignocellulosic biomass used in the method described here can be wood, in the form of pellets or, preferably, sawdust, olive stone or cereal straw.
    [0052] Preferably, the lignocellulosic biomass used is a solid with a size less than 4 mm, more preferably less than 2 mm. Consequently, this lignocellulosic biomass depolymerization method may comprise an additional step of crushing, grinding or similar procedure to obtain biomass particles with the indicated size.
    [0054] The lignocellulosic biomass depolymerization method described here allows the treatment of biomass in a semi-continuous process, that is, in a process where the different steps can be repeated cyclically and where, advantageously, cumbersome steps are not necessary. pressurization / depressurization of the system between each of the cycles. Preferably, in each cycle of the method an amount of biomass between 10% and 50% in dry weight is added with respect to the weight of the solvent medium; more preferably between 25% and 35% by dry weight relative to the total weight of the solvent medium. This biomass can comprise up to 50% water, an amount expressed by weight with respect to the total weight of lignocellulosic biomass. On those occasions when wet biomass is used, it should be understood that the amount of biomass added in each cycle is expressed in weight of dry biomass with respect to the total weight of the solvent medium.
    [0056] In this document, "solvent medium" should be understood as the liquid medium where the depolymerization reaction takes place. This solvent medium will always comprise an acid catalyst and solvents as disclosed in this document and, additionally, may contain compounds derived from the depolymerization of the lignin, when at least part of the liquid phase obtained in step e) of a previous cycle is being used.
    [0058] In preferred embodiments of the present invention, the solvent is selected from the group consisting of triethylene glycol (CAS 112-27-6), tripropylene glycol (CAS 24800-44-0), dipropylene glycol (CAS 25265-71-8), Levulinic acid (CAS 123-76-2) and any combination of the above.
    [0060] In addition to having suitable solvent properties to carry out the depolymerization of lignocellulosic biomass under the reaction conditions of the method described here, levulinic acid has the additional advantage that it can be manufactured from cellulose obtained by the method herein It is described.
    [0062] For its part, the acid catalyst will preferably be an organosulfonic acid, more preferably para-toluenesulfonic acid. The main advantage of this catalyst is that it has a very low pKa (it is a strong acid, like inorganics, although much less corrosive than other common inorganic acids such as hydrochloric or sulfuric acid) but its structure is organic and consequently dissolves very well in organic solvents.
    [0064] Subsequently, in step e) of the method described here, the solid, mostly cellulose, present in the enriched solvent medium obtained after the depolymerization reaction of step d) is separated. This solid-liquid separation can preferably take place by centrifugation, and even more preferably using a decanter centrifuge. Part or all of the enriched liquid medium obtained after this solid-liquid separation process can be used as a solvent medium for more lignocellulosic biomass, in particular using it as a solvent medium in step a) of a subsequent cycle of the method described in this document.
    [0066] The biomass depolymerization process takes place at atmospheric pressure, that is, without applying any type of external pressure, and a relatively moderate temperature, in particular between 150 and 200 ° C, which allows the method to be carried out in a semi-continuous form, since it is possible that the addition of biomass and extraction of the reaction mixture after depolymerization (cellulose and enriched solvent medium) from the reactor vessel takes place without the need to carry out pressurization and depressurization processes, thus facilitating the execution of the method described here compared to others previously used.
    [0068] Once the mixture of biomass and solvent medium, optionally enriched solvent medium, has reached a temperature in the established range, it is maintained for a minimum reaction period of 5 min, preferably between 5 min and 40 min and, more preferably between 5 min and 20 min, before proceeding to the solid-liquid separation of step e), where a solid (mainly cellulose) and a liquid medium enriched in compounds derived from the depolymerization of lignin are separated. Unexpectedly, it has been observed in the tests carried out that the depolymerization time of lignin is very fast, and can be as long as 5 min.
    [0070] The solid obtained in stage e), composed mainly of cellulose, can be directed to different post-treatment stages, depending on the intended use of this product. In particular, the cellulose obtained in the method described herein can be transformed into levulinic acid, one of the preferred solvents used in this lignocellulosic biomass depolymerization method.
    [0071] On the other hand, the enriched solvent medium obtained after this separation step can be used at least partially as a solvent medium in stage a) of a new cycle of the lignocellulosic biomass treatment method described herein. The use of at least part of this enriched solvent medium in a subsequent cycle of the method offers several advantages. These include an increase in the solubility of the lignin present in the biomass to be treated, which results in a reduction in reaction time and, additionally, a reduction in the cost of production, by not having to replace all the solvent medium in each of the lignocellulosic biomass treatment cycles.
    [0073] The enriched solvent medium that is not used in a subsequent cycle of the method of the present invention, either because only a part of this solvent medium is reused or, preferably, because the content of compounds derived from the depolymerization of lignin is high (for example , after carrying out several production cycles), it can be used to obtain biofuels according to procedures known in the sector.
    [0075] In short, with the method of the present invention it is achieved that the lignocellulosic biomass, preferably particles with a size less than 4 mm, more preferably less than 2 mm, and not necessarily dry, since the water that may be present will evaporate in the reaction conditions, dissolves in the specific combination of solvent and acid catalyst, at the specified working temperature and pressure, giving rise to different compounds that are easily separable and, therefore, usable separately, in a very reduced reaction time, in particular between 5 and 40 min and preferably between 5 and 20 min.
    [0077] The lignocellulosic biomass transformation reaction is catalyzed by an acid catalyst, in particular para-toluenesulfonic acid. In this way, through the effect of the solvent included in the solvent medium combined with the action of the catalyst, under the specified reaction conditions, the depolymerization of the biomass lignin is obtained and its conversion into a variety of compounds that remain dissolved. in the solvent medium. During this process, in particular, when the reaction takes place at a temperature of 165 ° C to 190 ° C, condensable gases are produced comprising water and furfural. In the method of the invention, the moisture content of the biomass (this can comprise up to 50% water, in dry weight relative to the weight of wet biomass) and the water generated in the hemicellulose depolymerization and dehydration reactions it evaporates and can be collected downstream in a condensation tower, so it is not strictly necessary for the biomass to be treated to be completely dry.
    [0079] Another object of the invention is a suitable installation to carry out the method described in this document, where the installation comprises:
    [0080] i) a biomass feed system (in particular, from a storage hopper);
    [0081] ii) a reactor vessel connected to the biomass feed system, where the reactor comprises stirring means, heating means to reach a temperature of up to 200 ° C, and distillation means with at least one gas outlet, and where the vessel it additionally comprises at least one outlet, preferably located at the bottom of the reactor, configured to extract a liquid medium or solid-liquid mixture from the reactor vessel;
    [0082] iii) at least one heat exchanger connected to a cooler (condenser) connected to the gas outlet of the reactor; Y
    [0083] iv) a decanter centrifuge connected to the reactor outlet by means of at least one heat exchanger, suitable for reducing the temperature of the solid-liquid mixture, preferably to less than 140 ° C; and preferably with a second connection that allows the return of the separated liquid phase (ie, the enriched solvent medium) to the reactor vessel.
    [0085] Thus, distillation / condensation means exit from the reactor vessel for the continued extraction of the water containing the biomass, the dehydration water of the hemicellulose monomers and the furfural that is formed in this process. In general, in the installation, the depolymerization of the biomass is obtained in its basic constituents, which are obtained separately at different points of the same.
    [0087] Thanks to the design of this lignocellulosic biomass transformation plant, through a depolymerization process, it can work in semi-continuous mode, that is, without the need to stop the plant, or to carry out heating-cooling or pressurization-depressurization cycles of the reactor vessel. included in the installation. Due to its configuration, this plant (also called installation in this document) can be used to depolymerize solid biomass containing lignocellulose according to the method described above.
    [0088] Preferably, the minimum diameter of the solution reactor vessel is 2 meters and its height is 3 meters. In a generic way and without assuming a limiting aspect, the reactor can have conventional safety measures, in addition to a temperature and pressure gauge, pressure regulating valve, rupture disc, additional safety valve, or other components. conventional.
    [0090] Additionally, the installation can have several heat exchangers, in particular shell tubes, whose mission is to reduce the energy consumption of the process as much as possible, which in this case can be provided in a boiler that generates thermal oil by combustion of pellets or other biomass. In particular, the configuration of the different heat exchangers of the installation described here makes it possible to take advantage of the heat of the solid-liquid mixture extracted from the reactor vessel, to adjust the temperature of the enriched solvent medium before incorporating it back into the reactor vessel to start the next cycle of the method described here.
    [0092] This preferred installation, due to its configuration and design, is ideal for carrying out the depolymerization method of lignocellulosic biomass, in any of its variants, in such a way that working in semi-continuous mode the desired reaction of the biomass is obtained, without the need for stop the system or carry out heating-cooling or pressurization-depressurization cycles of the reactor vessel included in the installation, as occurs in typical batch systems that operate at a pressure higher than atmospheric.
    [0094] BRIEF DESCRIPTION OF THE FIGURES
    [0096] Figure 1. Installation for the transformation of solid biomass containing lignocellulose to achieve its depolymerization, according to the preferred embodiment of the present invention, where the following elements are shown:
    [0097] 1 - reactor vessel
    [0098] 2 - biomass feeding system
    [0099] 3 - means of agitation
    [0100] 4 - gas outlet from the reactor vessel
    [0101] 5 - reactor vessel outlet
    [0102] 6a, 6b - coolers
    [0103] 7 - centrifuge
    [0104] 8a, 8b, 8c, 8d, 8e - heat exchangers
    [0105] 9 - boiler
    [0106] 10 - solids outlet from the centrifuge
    [0107] 11 - exit of enriched solvent medium from the centrifuge
    [0108] 12 - inlet of liquids to the reactor vessel
    [0110] In particular, this installation comprises a reactor vessel (1), where the solvent and the acid catalyst are introduced to carry out the method described in this document. This reactor vessel (1) is connected to a lignocellulosic biomass feed system (2), for example, from a storage hopper. Additionally, this container comprises stirring means (3), heating means to reach a temperature of up to 200 ° C, in particular the exchanger system described below, distillation means with a gas outlet (4) from the container reactor, and another outlet (5) configured to extract a liquid medium or solid-liquid mixture from the reactor vessel (1), preferably this outlet (5) is located at the bottom of the reactor vessel (1).
    [0112] The configuration of this installation allows the recirculation of the solvent medium from the outlet (5) of the reactor vessel, by means of a pump and a three-way valve, through a first exchanger (8a) which, in turn, is thermally connected to a boiler (9) of thermal oil, so that the solvent medium reaches a temperature between 150 ° C and 200 ° C, preferably between 165 ° C and 190 ° C. The configuration of this installation also makes it possible to direct the solid-liquid mixture obtained after the depolymerization reaction from the outlet (5) of the reactor vessel towards a decanter centrifuge (7), passing through several heat exchangers (8b, 8c). In the particular embodiment shown in figure 1, the outlet (5) of the reactor vessel is connected, by means of a pump and three-way valve, to a second exchanger (8b) which, in turn, is connected to a third exchanger (8c) which, in turn, is connected to a centrifuge (7). Furthermore, this third exchanger (8c) is thermally connected to a first cooler (6a) to allow the solid-liquid mixture to be cooled to a temperature no higher than 140 ° C before it enters the centrifuge (7).
    [0114] As mentioned above, the installation comprises a centrifuge (7), in particular a decanter centrifuge, which allows the solid-liquid mixture to be separated, obtaining a solid phase (mostly cellulose) and a liquid phase (solvent medium enriched in depolymerization compounds. of lignin). In this installation, the centrifuge (7) has a solid outlet (10), and a liquid outlet (11) connected to a fourth exchanger (8d), which is connected to the first exchanger (8a) and, finally, to the liquid inlet (12) into the reactor vessel (1). In order to take advantage of the heat from the solid-liquid mixture to heat the enriched solvent medium, the fourth exchanger (8d) is thermally connected to the second exchanger (8b).
    [0116] On the other hand, the installation described in this document may comprise means of distillation and condensation of the furfural produced in the depolymerization reaction of lignocellulosic biomass. In particular, the installation described in figure 1 comprises a gas outlet (4) of the reactor vessel, a cooler (6b) and a heat exchanger (8e) with a liquid outlet to collect the furfural, or furfural mixture. / water, condensed in this procedure.
    [0118] As mentioned above, the heat exchangers (8a, 8b, 8c, 8d, 8e) are preferably carcass tubes.
    [0120] EXAMPLES OF REALIZATION
    [0121] EXAMPLE 1:
    [0123] A preferred embodiment of the invention is described below, by way of example and without limitation, in which the depolymerization method is shown from solid biomass containing lignocellulose, specifically wood in the form of sawdust, to produce a fraction solid (cellulose), another liquid (derived from the depolymerization of lignin dissolved in the solvent medium) and another gaseous that will later condense to liquid (water and furfural).
    [0125] From the parameters indicated above, the following are selected for this preferred embodiment:
    [0127] • The selected solvent is levulinic acid.
    [0128] • The sawdust, during the grinding of the wood, must pass through a 1.5 mm grid. of light. • The selected catalyst is p-Toluen Sulfonic acid, in a concentration up to 1% by weight with respect to the dry weight of biomass.
    [0129] • The biomass concentration is 30% in dry weight with respect to the weight of the solvent medium, that is, of the mixture of solvent and acid catalyst.
    [0130] • The reaction temperature is kept at 180 ° C.
    [0131] The reaction pressure is atmospheric.
    [0132] The residence time of the biomass and the solvent-catalyst mixture at this temperature is 10 minutes.
    [0133] At the temperature set in this example of 180 ° C, the hemicellulose degrades and dehydrates to produce furfural, which distills along with the water that is formed. They are subsequently cooled and collected by condensation downstream of the installation.
    [0134] After the 10 minutes have elapsed at the indicated temperature, the solid-liquid mixture is withdrawn from the reactor vessel and cooled to a maximum temperature of 140 ° C. This mixture is then centrifuged using a decanter centrifuge, to separate the solid present in the reaction mixture (mostly cellulose) from the enriched solvent medium (liquid), which in turn is directed back into the container. reactor to start the next cycle of the method under the conditions indicated above.
    [0135] Cellulose can be directed to subsequent whitening or hydrolysis treatments.
    权利要求:
    Claims (8)
    [1]
    1. - A depolymerization method of lingocellulosic biomass that comprises:
    a) obtaining a solvent medium comprising an acid catalyst and a solvent selected from the group consisting of glycol ether, levulinic acid, and a combination of the foregoing;
    b) adjusting the temperature of the solvent medium of step a) between 150 ° C and 200 ° C;
    c) adding lignocellulosic biomass to the solvent medium of step b), maintaining stirring, atmospheric pressure and the temperature between 150 ° C and 200 ° C;
    d) maintaining the conditions established in step c) for a reaction period of at least 5 minutes, under conditions that allow the distillation of volatile compounds from the solvent medium; Y
    e) solid-liquid separation of the solid present in the enriched solvent medium obtained after step d).
    [2]
    2. - The method according to claim 1, where steps b), c) and d) take place at a temperature between 165 ° C and 190 ° C to separate the furfural obtained from the lignocellulosic biomass by distillation, and the method It comprises an additional stage d-1) where the condensation of the furfural present in the distillate takes place by cooling it.
    [3]
    3. - The method according to any one of claims 1 to 2, where steps a) to e) are repeated n times, n being a number greater than 1, and at least part of the enriched solvent medium obtained after solid-liquid separation from step e) of a cycle is used as the solvent medium in step a) of a subsequent cycle.
    [4]
    4. - The method according to any one of claims 1 to 3, wherein the lignocellulosic biomass is selected from the group consisting of wood, olive stone and cereal straw.
    [5]
    5. - The method according to any one of claims 1 to 4, wherein the lignocellulosic biomass is a solid with particles smaller than 4 mm.
    [6]
    6. - The method according to any one of claims 1 to 5, wherein the concentration of lignocellulosic biomass added in step c) is between 10% and 50% in dry weight relative to the total weight of the solvent medium.
    [7]
    7. - The method according to any one of claims 1 to 6, wherein the solvent is glycol ether and is selected from the group consisting of triethylene glycol, tripropylene glycol, diethylene glycol and a combination of the above.
    [8]
    8. - The method according to any one of claims 1 to 7, wherein the acid catalyst is para-toluenesulfonic acid.
    method according to any one of claims 1 to 8, wherein the reaction period in step d) is from 5 min to 20 min.
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    同族专利:
    公开号 | 公开日
    ES2819834B2|2021-09-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20110144359A1|2009-12-16|2011-06-16|Heide Evert Van Der|Method for producing furfural from lignocellulosic biomass material|
    WO2011149341A1|2010-05-25|2011-12-01|Technische Universiteit Delft|Process for the treatment of lignocellulosic biomass|
    CN108530404A|2018-03-23|2018-09-14|中国科学院广州能源研究所|A kind of method of depolymerization biomass coproducing furfural, cellulose and lignin|
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