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    • 专利摘要:
    PROCESS TO SEPARATE FURFURAL FROM A WATER LIQUID PHASE, AND USE OF AN AROMATIC HYDROCARBON COMPOUND. A process for the separation of furfural from a liquid aqueous phase comprising furfural and one or more organic acids, the process of which comprises a) a step of extracting furfural from a liquid aqueous phase into a liquid aromatic phase comprising a or more aromatic hydrocarbon compounds to obtain an organic phase comprising furfural and one or more aromatic hydrocarbon compounds.
    公开号:BR112012029213B1
    申请号:R112012029213-7
    申请日:2011-06-22
    公开日:2020-11-03
    发明作者:Johannes Pieter Haan
    申请人:Shell Internationale Research Maatschappij B.V；
    IPC主号:
    专利说明:

    TECHNICAL FIELD OF THE INVENTION
    [001] The present invention relates to a process for the separation of furfural from a liquid aqueous phase, which comprises furfural and one or more organic acids. BACKGROUND OF THE INVENTION
    [002] Furfural, also known as Furan-2-carbaldehyde, is a valuable intermediary in the production of sustainable biofuels. Biofuels are fuels, which can be derived from biological sources. The use of such biofuels results in a reduction in greenhouse gas emissions. Furfural can conveniently be produced from biomass. It is, for example, produced in the liquefaction of lignocellulosic material.
    [003] After liquefaction of the lignocellulosic material, it is desirable to separate furfural from the total aqueous product produced. The separation of furfural by distillation, however, is problematic, as furfural can form azeotropes with water in the total aqueous product.
    [004] Alternative approaches to the recovery of furfuraldehyde include liquid-liquid extraction processes.
    [005] US 4533743 describes a process for the production of furfuraldehyde. She describes that state of the art biomass acid hydrolysis processing techniques can disrupt pentosans, a major constituent of biomass hemicellulose, in pentoses. The hot pentose is subsequently reacted, in the presence of a mineral acid catalyst, in a buffer flow reactor, at a temperature in the range from 220 ° C to 300 ° C, so that furfural is produced . The furfuraldehyde produced is optionally extracted using a furfuraldehyde solvent essentially immiscible in water, which does not form an azeotrope with the furfuraldehyde.
    [006] As suitable solvents, mention is made, among others, of the highest boiling aromatic products, such as diethyl benzene, dipropyl benzene, dimethylethyl benzene, butyl benzene, tetraline and isophorone; aromatics, such as toluene; halogenated aromatics; and also halogenated alkanes.
    [007] US 6,441,202 describes a method for producing sugars through acid hydrolysis of biomass and subsequently subjecting sugars to dehydration, so that a hydrolyzate is formed, comprising heterocyclic compounds, such as furfural and hydroxymethyl. furfural and acid. Subsequently, the heterocyclic compounds are extracted from a hydrolyzate by means of a hydrocarbon. The acid can include an organic acid or an inorganic acid, such that, for example, sulfuric acid and hydrocarbon can be, for example, toluene. FR 2411184 also describes a process for preparing furfuraldehyde. It describes subjecting a sugar solution to acid dehydration, so that xylose is converted into furfural. Furfural is extracted with a solvent. Suitable solvents, among others, include toluene, xylene, methyl naphthalene and benzaldehyde.
    [008] J. Croker et al. describe a process for the liquid extraction of furfural from an aqueous solution (see his article “liquid extraction of furfural from aqueous solution” by John R. Croker and Ron G. Bowrey, Ind. Eng. Chem. Fundam., 1984 , vol. 23, pages 480-484). They describe the extraction for water-furfural methyl isobutyl ketone, water-furfural-isobutyl acetate and water-furfural-toluene systems.
    [009] In the prior art methods for the extraction of furfural, however, the starting solution is a solution, which comprises only a limited amount of components, such as, for example, furfural, water and, in a optional, sugars and / or an acid such as sulfuric acid. SUMMARY OF THE INVENTION
    [0010] It has now been found, in an advantageous way, that furfural can also be selectively extracted from liquid-liquid extraction from a complex starting solution, which comprises not only furfural, water and optionally sugars, but also a complex combination of one or more organic acids.
    [0011] The present invention therefore provides a process for the separation of furfural from a liquid aqueous phase, which comprises furfural and one or more organic acids, the process of which comprises a stage of: a) extracting furfural from from the liquid aqueous phase to the interior of a liquid aromatic phase, comprising one or more aromatic hydrocarbon compounds, so that a liquid organic phase, comprising furfural and one or more aromatic hydrocarbon compounds, is obtained.
    [0012] It has now been verified that the contact of the liquid aqueous phase, which comprises furfural and one or more organic acids, with a liquid aromatic phase, which comprises one or more aromatic hydrocarbon compounds, allows it to be possible to extract, from in a selective way, furfural from the liquid aqueous phase to the interior of the liquid aromatic phase, leaving the deplective aqueous phase in furfural, but still rich in organic acid.
    [0013] The present invention thus makes it possible to directly extract furfural from a liquid aqueous phase, which comprises furfural and one or more organic acids, formed through catalyzed biomass hydrolysis.
    [0014] The selective extraction of furfuraldehyde from organic acids in an aqueous environment has not been previously suggested. BRIEF DESCRIPTION OF THE DRAWINGS
    [0015] Figure 1 presents a schematic diagram of a process for the extraction of furfural according to the invention.
    [0016] Figure 2 presents a schematic diagram of a process for the extraction of furfural according to the invention, with the recovery of the extraction solvent. DETAILED DESCRIPTION OF THE INVENTION
    [0017] In the process according to the present invention, furfural is extracted from a liquid aqueous phase, which comprises furfural and one or more organic acids.
    [0018] By a liquid phase, a phase is understood here, which is liquid at extraction temperature and pressure. A liquid aqueous phase is understood to mean a liquid phase, which comprises at least water.
    [0019] In one embodiment, the liquid aqueous phase is produced through hydrolysis catalyzed by biomass acid, preferably from lignocellulosic material. Preferably, the liquid aqueous phase is obtained by liquefying lignocellulosic material. As used herein, lignocellulosic material refers to a material, which comprises lignin, cellulose and hemicellulose.
    [0020] Without wishing to be limited to any type of theory, it is believed that the liquefaction of lignocellulosic material may comprise the cleavage of covalent bonds in the cellulose, hemicellulose and lignin present and / or the cleavage of covalent bonds between lignin, hemicelluloses and / or cellulose. As a result, acids, such as formic acid, acetic acid and / or levulinic acid can be formed, together with sugars and, optionally, lignin degradation products. The cellulose present in the lignocellulosic material can be converted into a sugar containing six carbon atoms, which is degraded in the presence of an acid catalyst, so that the hydroxymethyl furfural is produced, and then additionally hydrolyzed, in order to provide the levulinic acid. The hemicellulose present in the lignocellulosic material can be converted into a five-carbon sugar, which is broken down in order to provide the furfural.
    [0021] Lignocellulosic material can be obtained from a variety of plants and plant materials, including agricultural waste, forest waste and sugar processing residues. Examples of suitable lignocellulosic materials include agricultural waste, such as corn fodder, soy fodder, corn cobs, rice straw, rice husks, oat husks, corn fiber, cereal straws, such as wheat, barley, rye and oat straw; grasses; forest products, such as wood and wood-related materials, such as sawdust; waste from sugar processing, such as bagasse and beet pulp; or mixtures thereof.
    [0022] The liquefaction of the lignocellulosic material can be carried out in a way known per se to the person skilled in the art, in a way that is suitable for such a purpose. The liquefaction of the lignocellulosic material may suitably comprise the hydrolysation of the lignocellulosic material in the presence of an acid catalyst. Examples of suitable acid catalysts include mineral acids, such as sulfuric acid, para-toluenesulfonic acid and / or mixtures thereof; and organic acids, such as oxalic acid, formic acid, lactic acid, citric acid, trifluoroacetic acid and / or mixtures thereof. The temperature applied during hydrolysis can vary widely and is preferably in the range of 100 ° C to 300 ° C, and more preferably from 150 ° C to 250 ° C.
    [0023] In yet another embodiment, a lignocellulosic material is hydrolyzed in the presence of an acid catalyst acid, so that a liquid aqueous phase is prepared, comprising furfural and one or more organic acids, the liquid aqueous phase of which is subsequently used directly as the starting liquid aqueous phase of the process according to the invention, in the absence of additional recovery or concentration stages.
    [0024] The process of the invention is therefore particularly advantageous for the extraction of furfural and one or more organic acids, the liquid aqueous phase of which is produced by acid-catalyzed hydrolysis of a lignocellulosic material.
    The liquid aqueous phase preferably comprises more than or equal to 0.1% by weight, and even more preferably more than or equal to 0.5% by weight, and still more preferably more than or equal to 1.0% by weight of furfuraldehyde and preferably less than or equal to 30.0% by weight and more preferably less than or equal to 20% by weight, and even more preferably less than or equal to 10.0% by weight, of furfural, based on the total weight of the liquid aqueous phase.
    [0026] The liquid aqueous phase further preferably comprises more than or equal to 0.1% by weight, even more preferably more than or equal to 0.5% by weight, and even more preferably more than or equal to 1.0%, by weight, of one or more organic acids and preferably less than or equal to 30.0%, by weight, more preferably less than or equal to 30.0% by weight, and more preferably less than or equal to 25.0% by weight, and even more preferably less than or equal to 20.0% by weight weight of one or more organic acids, based on the total weight of the liquid aqueous phase.
    [0027] Preferably, the one or more organic acids are selected from the group of levulinic acid, acetic acid, formic acid and mixtures thereof. Preferably, the liquid aqueous phase essentially comprises only the organic acids selected from the group of levulinic acid, acetic acid, formic acid, and mixtures thereof. In still a preferred embodiment, the liquid aqueous phase comprises at least levulinic acid.
    [0028] A liquid aromatic phase is understood to mean a liquid phase, which comprises at least one aromatic hydrocarbon compound. In the process according to the invention, the liquid aromatic phase can comprise one or more aromatic hydrocarbon compounds.
    [0029] As used herein, an aromatic hydrocarbon compound is understood to be a compound, which comprises a benzene or naphthalene ring, the ring of which is optionally substituted by one or more alkyl groups. The term "alkyl" includes both straight chain and branched chain alkyl groups. If substituted, the benzene or naphthalene ring is preferably substituted by one to four, more preferably by one or two alkyl groups. Preferably, the alkyl group contains from 1 to 6, and more preferably from 2 to 4 carbon atoms. Preferably, the liquid aromatic phase includes benzene substituted by C1-6 alkyl, naphthalene substituted by C1-6 alkyl or a mixture thereof.
    [0030] The one or more aromatic hydrocarbon compounds are suitably capable of acting as a solvent, in which furfural is soluble (at an extraction temperature and pressure) and are preferably substantially immiscible in water. A substantially water-immiscible aromatic hydrocarbon compound refers to an aromatic hydrocarbon compound having a water solubility of less than 500 mg / kg, at temperature (20 ° C) and pressure (1 bar absolute) (0.1 MPa) environments.
    [0031] Preferably, the liquid aromatic phase comprises one or more aromatic hydrocarbon compounds having a higher boiling point than furfural. The use of one or more aromatic hydrocarbon compounds having a higher boiling point than furfural advantageously facilitates the recycling of the aromatic hydrocarbon compound, reducing the amount of energy required, and thereby improving efficiency cost of the invention process.
    [0032] It has been found that, although toluene (methyl benzene) can selectively extract furfural from a liquid aqueous phase, which comprises furfural and one or more organic acids, the fact that it has a boiling point (111 ° C), which is below that of furfural (162 ° C), makes recycling expensive.
    Preferred aromatic hydrocarbon compounds include alkyl benzenes having an alkyl side chain with at least 2 carbon atoms, and which has a boiling point above that of furfural, such as butyl benzene (boiling point 183 ° C ), pentyl benzene (boiling point 205 ° C) and hexyl benzene (boiling point 226 ° C).
    [0034] Naphthalene has a boiling point (218 ° C), which is higher than that of furfural, indicating that it must be quite suitable for the extraction of furfural from an aqueous phase, which comprises furfural. However, the practical applications of naphthalene for use as an extraction solvent (that is, as a liquid aromatic phase) according to the present invention are limited, as naphthalene is a solid below 80 ° C, meaning that liquid / liquid extractions using naphthalene are not feasible below this temperature.
    [0035] Preferred aromatic hydrocarbon compounds include alkyl substituted naphthalenes, which are melted at lower temperatures than naphthalene. In a particular embodiment, the aromatic hydrocarbon compound comprises 1-methyl naphthalene.
    [0036] Aromatic hydrocarbon mixtures can also suitably be used in the process of the invention. In yet another embodiment, the liquid aromatic phase comprises a mixture of naphthalene and 1-methyl naphthalene. By dissolving naphthalene in 1-methyl naphthalene, which is liquid at room temperature with a boiling point of 241 ° C, a high extraction selectivity can be achieved, while avoiding the practical problem associated with use of naphthalene alone.
    [0037] In a preferred embodiment, the liquid aromatic phase essentially consists of a mixture of naphthalene and 1-methyl naphthalene. Preferably, a mixture with a weight ratio of naphthalene to 1-methyl naphthalene in a range of 1: 5 to 5: 1, more preferably 1: 4 to 4: 1, and preferably even more preferred from 1: 2 to 2: 1. The liquid aromatic phase preferably comprises more than or equal to 40% by weight, more preferably more than or equal to 50% by weight, and even more preferably more than or equal to 60%, by weight, of one or more aromatic hydrocarbon compounds, based on the total weight of the liquid aromatic phase. For practical purposes, the liquid aromatic phase may comprise equal to, or less than 100%, by weight, of one or more aromatic hydrocarbon compounds, based on the total liquid aromatic phase. The liquid aromatic phase further preferably comprises less than 40% by weight of non-aromatic hydrocarbon compounds, even more preferably less than 10% by weight of non-aromatic hydrocarbon compounds, with based on the total liquid aromatic phase. Even more preferably, the liquid aromatic phase is essentially free of non-aromatic hydrocarbon compounds. Examples of such non-aromatic hydrocarbon compounds include paraffins (branched), olefins (branched) and naphthenics.
    [0038] Furfural can be extracted from the liquid phase, which comprises furfural and one or more organic acids, by contacting the liquid aqueous phase with the liquid aromatic phase, which comprises one or more aromatic hydrocarbon compounds. The liquid aromatic phase can be added to the liquid aqueous phase or the liquid aqueous phase can be added to the liquid aromatic phase. Preferably, the liquid aromatic phase is added to the liquid aqueous phase. The contact of the liquid aqueous phase and the liquid aromatic phase can be carried out in batch or in a continuous manner. When carried out in a continuous manner, the contact of the liquid aqueous phase and the liquid aromatic phase can be carried out in a countercurrent, co-current or transversal current mode, with respect to each other. Preferably, the liquid aqueous phase and the liquid aromatic phase are contacted with each other, in a countercurrent mode, more preferably with the highest density liquid stream being introduced at the top of a column of extraction and the lower density liquid stream being fed to the bottom of the extraction column. Alternatively, several mixer / settler units, in series, can be used. By contacting the liquid aqueous phase and the liquid aromatic phase, two phases can be formed. The furfural present in the liquid aqueous phase is selectively extracted into the liquid aromatic phase, forming a liquid organic phase and leaving the depleting liquid aqueous phase in furfural. The organic acid (s), present in the liquid aqueous phase, remain in the liquid aqueous phase, leaving the liquid aqueous phase rich in organic acid (s). By a liquid organic phase is meant a liquid phase, which comprises one or more organic compounds. The liquid organic phase formed comprises furfural and one or more aromatic hydrocarbon compounds. The liquid organic phase formed preferably comprises in a range of from 0.2% by weight to 40.0% by weight, and more preferably in a range of from 1% , 0% by weight to 20.0% by weight of furfuraldehyde based on the total weight of the liquid organic phase.
    [0039] Preferably, the liquid aqueous phase, which comprises furfural and one or more organic acids, and the liquid aromatic phase, which comprises one or more aromatic hydrocarbon compounds, are contacted in a ratio of the liquid aqueous phase to the liquid aromatic phase in a range from 2: 1 to 1: 5.
    [0040] Pressure and temperature can be selected in such a way that the liquid aqueous phase and the liquid aromatic phase remain in the liquid state. Preferably, the process according to the invention is carried out at a temperature of less than, or equal to 200 ° C, more preferably at a temperature of less than, or equal to 150 ° C, and in a manner even more preferred at a temperature of less than or equal to 90 ° C and at a temperature of more than or equal to 15 ° C, and even more preferably at a temperature of more than or equal to 20 ° C . The process according to the invention is conducted, more preferably, at a pressure of less than or equal to 25 bar (2.5 MPa) absolute, more preferably of less than or equal to 10 bar (1 MPa), and even more preferably at ambient pressure (1 bar absolute) (0.1 MPa).
    [0041] After the extraction of furfural from the liquid aqueous phase into the liquid aromatic phase, the depleted liquid phase in furfural formed can be separated and removed from the formed liquid organic phase, using conventional techniques, such as separation gravitational (eg sedimentation).
    [0042] The depurative liquid aqueous phase in furfuraldehyde is preferably removed from the formed organic liquid phase and preferably recycled and reused, for example, in the lignocellulose acid catalyzed hydrolysis of a so that more furfural is provided in the liquid aqueous solution.
    [0043] Aromatic hydrocarbon compounds are preferably recovered from the liquid organic phase formed and recycled for use in the extraction process.
    [0044] In a preferred embodiment, the process according to the invention subsequently comprises an additional stage, in which furfural is recovered from the liquid organic phase.
    [0045] The separation of furfuraldehyde extracted from the liquid organic phase, inside which it is extracted, can be achieved through any techniques, known to be suitable for this purpose. A preferred technique is distillation. An advantage regarding the use of one or more aromatic hydrocarbon compounds having a higher boiling point than furfural is that the extracted furfural can be evaporated, instead of the aromatic hydrocarbon compound (s). As furfural is generally present in a smaller amount than aromatic hydrocarbon compound (s), this requires less energy. In addition, the use of one or more higher boiling aromatic hydrocarbon compound (s) allows a lower ratio of the liquid aqueous phase to the liquid aromatic phase to be used in the process of the invention, without incurring any greater energy overload in the recovery stage. This means that more than one aromatic hydrocarbon compound per furfural unit is available in the extraction tower, so that furfuraldehyde is removed from the liquid aqueous phase. In addition, the separation of furfuraldehyde from the liquid organic phase by removing furfuraldehyde (through evaporation from the top of the distillation column), so as to make a liquid aromatic phase again provide the advantage of that the formation of furfuraldehyde condensation products is minimized, leading to a product of higher purity.
    [0046] In still a preferred embodiment, the process according to the invention further comprises a stage, in which the recovered furfural is converted into a furfural derivative, such that, for example, methyl tetrahydrofuran or methyl furan, and in which this furfural derivative is mixed with one or more other combustible components in order to produce a biofuel.
    [0047] In yet another preferred embodiment, the process according to the invention further comprises a stage, in which furfural is decarbonylated to furan, the furan of which is subsequently hydrogenated to tetrahydrofuran and / or hydrated to butanediol. Tetrahydrofuran and butanediol can be used as a chemical.
    [0048] Thus, the present invention also provides a process for the production of tetrahydrofuran and / or butanediol, which comprises: - extracting furfural from a liquid aqueous phase, the liquid aqueous phase of which comprises furfural and optionally one or more organic acids, within an aromatic phase, the liquid aromatic phase of which comprises one or more aromatic hydrocarbon compounds, so that an organic phase, comprising furfural and one or more aromatic hydrocarbon compounds, is obtained; - recover furfural from the liquid organic phase, in order to obtain furfural; - decarbonylation of furfural to obtain furan; and - hydrogenating furan in order to obtain tetrahydrofuran and / or hydrating furan in order to obtain butane diol.
    [0049] The extraction stage and the recovery stage are preferably performed as described above.
    [0050] The decarbonylation of furfural can be carried out in the presence of a decarbonylation catalyst. The decarbonylation catalyst can be any decarbonylation catalyst, known to those skilled in the art as being suitable for decarbonylation.
    [0051] For example, the decarbonylation catalyst can comprise a metal oxide and one or more catalytic metals. Metal oxide catalysts, for example, based on iron, zinc, magnesium, chromium, cobalt, molybdenum or nickel, are preferably used at temperatures of 300 ° C to 500 ° C.
    [0052] In yet another example, the decarbonylation catalyst may comprise supported noble metals, such as Pd / AECb. The supported noble metal catalysts are preferably used at a temperature of 240 ° C to 400 ° C, under a flow of H2.
    [0053] In yet another example, decarbonylation is performed, in liquid phase, in the absence of H2, using Pd catalysts supported on Alumina or Carbon and K2CO3 as a cocatalyst, preferably in a range from 100 ° C to 250 ° C.
    [0054] A subsequent hydrogenation of furan to tetrahydrofuran can be performed in the presence of a Ni catalyst.
    [0055] Figures 1 and 2 show diagrams of the process for two modalities of the process according to the invention. In the embodiment shown in Figure 1, a stream of liquid aqueous phase, comprising furfural and at least one of levulinic acid, formic acid and acetic acid, the stream of which is obtained from an acid-catalyzed hydrolysis of lignocellulosic material, flow ( 1), is directed to the extraction column (3). A liquid aromatic phase (2) is also introduced into the extraction column (3). In the modality shown, the liquid aqueous phase and the aromatic phase are introduced into the extraction column, at opposite ends, and flow in a countercurrent mode, with respect to each other, the highest density liquid stream (liquid aqueous phase) ) being introduced at the top of the column and the lower density liquid stream (liquid aromatic phase) being introduced at the bottom of the extraction column (3). In the extraction column (3), furfural is extracted from the liquid aqueous phase into the liquid aromatic phase, in order to provide a furfural-depleting liquid aqueous phase and a liquid organic phase, which comprises furfural and one or more aromatic hydrocarbon compounds. These two phases have different densities and can be separated through gravitational separation, as shown in Figure 1, in which the heavier liquid aqueous phase, depleting in furfural, is extracted from the bottom of the extraction column (flow 5) and the lighter liquid organic phase, enriched in furfural (flow 4), is removed as the aerial product. In the modality shown in Figure 2, the extraction process is performed using an aromatic hydrocarbon compound having a higher boiling point than furfural. The liquid organic phase, enriched in furfural, and comprising these aromatic hydrocarbon compounds having a higher boiling point than furfural (4a), is then supplied to a distillation column (6), where the furfural point lower (and therefore more volatile) boiling is separated from the higher-boiling aromatic hydrocarbon compound by distillation. Furfural is obtained as a vapor (flow 7) in the aerial part of the distillation column and the vapor is condensed to form the liquid furfural (not shown). The aromatic hydrocarbon compound is removed from the bottom of the distillation column (flow 8) and recycled back to the extraction column as (part of) the aromatic liquid phase 1 (2).
    [0056] Throughout the description and claims in this report, the words "understand" and "contain" and variations of the words, for example, "understanding" and "understand" mean "including, but not limited to", and do not exclude other portions, additives, components, whole or stages. EXAMPLES
    [0057] The invention will now be further illustrated by means of the following non-limiting examples.
    [0058] Abbreviations used in the examples below include: AR = Liquid Aromatic Phase AQ = Liquid Water Phase OR = Liquid Organic Phase FF = Furfural LA = Levulinic Acid AA = Acetic Acid FA = Formic Acid HS = Hydrolyzate Feed Solution T = Temperature Example 1: Extraction of furfural using alkyl benzene as a liquid aromatic phase: (i) Preparation of the Hydrolyzate Feed Solution
    [0059] 1000 ml of artificial lignocellulosic hydrolyzate feed solution (also referred to as “hydrolyzate” or HS) was prepared according to Table 1. Table 1: Hydrolyzate feed solution for Example 1:
    (ii) Extraction using butyl benzene, pentyl benzene or hexyl benzene as the liquid aromatic phase:
    [0060] The hydrolyzate (such as the liquid aqueous phase) (AQ) and an aromatic hydrocarbon compound (which forms the liquid aromatic phase (AR)), as indicated in Tables 2a, 2b, and 2c, were mixed in one together, in the following portions, by weight, 50: 25, 50:50, and 50: 100 g. The extraction took place in a 500 ml bottle, in a stirring device, at room temperature (about 20 ° C), for 30 minutes. An emulsion was then obtained. The emulsion was poured into a separating funnel, in which a liquid aqueous phase and a liquid organic phase were rapidly separated, the liquid aqueous phase formed being more dense. The two phases were collected in labeled bottles and their contents were analyzed.
    [0061] The above experiments were repeated at 60 ° C, using a boiling flask with a reflux cooler connected. The temperature was maintained by placing the bottle in an oil bath, with a temperature controller connected to a hot plate, which heats the oil. Analyze
    [0062] A mass balance was made for each extraction. In addition, the distribution ratio (Kd) of furfural (FF) was calculated by dividing the furfural content in the liquid organic phase (weight / wt%) by the furfural content in the liquid aqueous phase (weight / wt%) . The distribution ratios (Kd) of levulinic acid (LA), acetic acid (AA) and formic acid (FA) were calculated in an analogous way.
    [0063] The water content was determined using a Schott Titroline KF volumetric titrator, which uses the Karl Fischer method. The content of levulinic acid, formic acid and acetic acid in the liquid organic phase, from the experiments conducted at 60 ° C, was analyzed using an IEC. Furfural and aromatic hydrocarbon content were measured using a GC (Trace GC Ultra). Results
    [0064] The results obtained for the extractions using butyl benzene, pentyl benzene and hexyl benzene as the liquid aromatic phase (AR) are presented in Tables 2a-2c, respectively. The first line of each table shows the composition of the hydrolyzate (HS) feed solution used, the subsequent lines show the results obtained for the different liquid phases, after extraction in an alternative mode (first the liquid aqueous phase (AQ) and secondly the liquid organic phase (OR) for a ratio, by weight, of the aromatic liquid / hydrolyzate phase (AR / HS) and temperature (T). Table 2a: Butyl benzene as the liquid aromatic phase (AR)
    Table 2 b: Pentyl benzene as the liquid aromatic phase (AR)
    Table 2 c: Hexyl benzene as the liquid aromatic phase (AR)

    [0065] From the results presented it can be seen that all three alkyl benzenes, such as the liquid aromatic phase, were found to have high selectivity for furfural, with Kds of between 1.46 (butyl benzene, 25 ° C) and 1.01 (hexyl benzene, 25 ° C). The results obtained for extractions carried out at 25 ° C and 60 ° C were similar, indicating that all three alkyl benzenes have a low sensitivity to temperature. The Kd values for the other components present in the hydrolyzate (acetic acid, formic acid, levulinic acid) and are all approximately equal to zero. The aromatic hydrocarbon compounds in the liquid phases used are, therefore, selective for furfural, compared to other components in the hydrolyzate. (iii) Extraction using toluene as the liquid aromatic phase:
    [0066] Extractions using toluene as the liquid aromatic phase at 25 ° C were carried out, as described above, in various reasons, by weight, from liquid aromatic phase (AR) to the hydrolyzate (HS) and the results that following have been obtained. Table 3a: Toluene as the liquid aromatic phase (AR) at 25 ° C:
    Table 3b: Toluene as the liquid aromatic phase (AR) at 25 ° C
    Table 3c: Toluene as the liquid aromatic phase (AR) at 25 ° C

    [0067] From the results, it can be seen that toluene at 25 ° C is also selective for furfural. A distribution coefficient (kd) for furfuraldehyde of more than 3 is obtained, but the (kd) values for the other components of the hydrolyzate are all approximately equal to zero.
    [0068] Although toluene, like the liquid aromatic phase, can selectively extract furfural from the hydrolyzate (like the liquid aqueous phase), more energy will be required because toluene has a lower boiling point than furfural, which means that in order to recover furfural, the volume of toluene will have to be evaporated. When using toluene as the liquid aromatic phase, furfural will then be taken from the bottom of the distillation column, preferably from the top (as in the case of longer-chain alkyl benzenes) and thus the furfural should be present at a higher concentration and at higher temperatures than if a higher boiling aromatic hydrocarbon compound were used, with conditions that tend to favor the production of unwanted furfural condensation products. Example 2: Extraction of furfural using naphthalene in methyl naphthalene (i) Preparation of the hydrolyzate feed solution
    [0069] 200 ml of an artificial lignocellulosic hydrolyzate feed solution (also referred to as “hydrolyzate” or HS) was prepared, having the following composition (see table 4): Table 4: Hydrolyzate feed solution for the Example 2:
    (ii) Preparation of the liquid aromatic phase:
    [0070] A solution of about 20% by weight of naphthalene in methyl naphthalene was prepared, having the following composition (see Table 4): Table 5: Liquid aromatic phase
    (iii) Extraction
    [0071] The hydrolyzate (such as the liquid aqueous phase) and the liquid aromatic phase were mixed together in the following weight ratios: 50: 25, 50:50 and 50: 100. The extraction was carried out in a boiling flask, with a reflux cooler, placed in an oil bath in a stirring device, for a period of 30 minutes, at a constant temperature of 60 ° C. An emulsion was then obtained.
    [0072] The emulsion was poured into a separating funnel, where a liquid aqueous phase and a liquid organic phase were quickly separated, the liquid aqueous phase formed being the most dense. The two phases were collected in labeled bottles and their contents were analyzed. (iv) Analysis
    [0073] The distribution ratio (Kd) of furfural, water content, organic acid content, furfural content and aromatic hydrocarbon compound content were determined according to the methods used in Example 1. (v) Results
    [0074] The results obtained using 21.4% naphthalene in methyl naphthalene as an aromatic liquid phase are shown in Table 6 below.
    [0075] As for Tables 2a-2c above, the first row of each table shows the composition of the hydrolyzate (HS) feed solution used. The subsequent lines present the results obtained for the different liquid phases after extraction in an alternative mode (first, the liquid aqueous phase (AQ) and secondly the liquid organic phase (OR)) for a given ratio of liquid aromatic phase / hydrolyzate (AR / HS) and temperature (T).
    [0076] The kd obtained for naphthalene in methyl naphthalene (Kd 3.0) is similar to that obtained when toluene is used and is approximately twice the value obtained for butyl benzene as a liquid aromatic phase. The kd values of the other components present in the hydrolyzate feed solution are zero or almost zero, demonstrating that naphthalene in methyl naphthalene is selective for the extraction of furfural. Table 6: Naphthalene solution in methyl naphthalene as the liquid aromatic phase (AR)
    Comparative example A: Extraction of furfural using 2-methyl tetrahydrofuran (2-MTHF) or cyclohexanone (i) Preparation of hydrolyzate feed solution
    [0077] An artificial lignocellulosic hydrolyzate feed solution (also referred to as the "hydrolyzate" or HS) was prepared, having the compositions as indicated in Tables 7a, 7b, 7c and 7d. (ii) Extraction using methyl tetrahydrofuran or cyclohexanone:
    [0078] The hydrolyzate (such as the liquid aqueous phase (AQ)) and 2-methyl tetrahydrofuran (1-MTHF) or cyclohexanone were mixed together in a weight ratio of 2-MTHF or cyclohexanone to hydrolyzate , as indicated in Tables 7a, 7b, 7c and 7d. The extraction was carried out in a 500 ml bottle, in a stirring device, at room temperature (about 20 ° C) for 30 minutes. An emulsion was then obtained.
    [0079] The emulsion was poured into a separating funnel, where a liquid aqueous phase (AQ) and a liquid organic phase (OR) were quickly separated, the liquid aqueous phase formed being the most dense. The two phases were collected in labeled bottles and their contents were analyzed.
    [0080] For cyclohexanone, the experiment was repeated at 60 ° C, using a boiling flask with a reflux cooler connected. The temperature was maintained by placing the bottle in an oil bath, with a temperature controller connected to a hot plate, which heats the oil. (iv) Analysis
    [0081] The distribution ratio (Kd) of furfural, levulinic acid, formic acid and sulfuric acid and the water content, levulinic acid content, formic acid content, furfural content were determined according to the methods used in the Example 1. (v) Results:
    [0082] The results obtained using 2-MTHF and cyclohexanone to extract furfural are shown in Tables 7a, 7b, 7c and 7d below. As can be seen from Tables 7a, 7b, 7c and 7d, extraction with 2 MTHF or cyclohexanone does not selectively extract furfural, but also extracts considerable amounts of levulinic and formic acid. : 2-Methyl tetrahydrofuran (2-MTHF) to extract furfural in one. ao o un, .. oo. that of Q.MTHF 0 for HS of 1.
    Table 7b: 2-Methyl tetrahydrofuran (2-MTHF) to extract furfuraldehyde at a temperature of 20 ° C and in a weight ratio of 2-MTHF to HS of 0.50.
    Table 7c: Cyclohexanone to extract furfural at a temperature of 20 ° C and a weight ratio of cyclohexane to HS of 1.34.
    Table 7d: Cyclohexanone to extract furfural at a temperature of 60 ° C and a weight ratio of cyclohexanone to HS of 1.40.

    [0083] As shown above, surprisingly, aromatic hydrocarbon compounds can be used to selectively extract furfural from a liquid aqueous phase, comprising furfural and one or more organic acids ( for example, formed by acid catalyzed hydrolysis of biomass), while other hydrocarbon compounds are not suitable for such use.
    权利要求:
    Claims (9)
    [0001]
    1. Process to separate furfural from a liquid aqueous phase, comprising furfural and one or more organic acids, comprising a stage of: a) extraction of furfural from the liquid aqueous phase (1) into a liquid aromatic phase (2) characterized by the fact that it comprises aromatic hydrocarbon compounds including a mixture of a naphthalene substituted by C1-6 alkyl with a benzene substituted by C1-6 alkyl or comprising a mixture of naphthalene and 1-methyl naphthalene to obtain an organic phase liquid (4) comprising furfural; wherein the liquid aqueous phase (1) comprises one or more organic acids selected from the group of levulinic acid, acetic acid, formic acid and mixtures thereof.
    [0002]
    2. Process, according to claim 1, characterized by the fact that the process also comprises a stage of: b) recovery of furfural from the liquid organic phase (4) obtained in stage a) to obtain furfural (7) .
    [0003]
    3. Process according to claim 2, characterized by the fact that the process further comprises a stage of: c) converting furfural (7) obtained in stage b) into a furfural derivative and mixing the furfural derivative with a or more other fuel components to produce a biofuel.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the liquid aqueous phase (1) is produced by acid-catalyzed hydrolysis of lignocellulosic material.
    [0005]
    Process according to any one of claims 1 to 4, characterized in that the liquid aqueous phase (1) comprises more than or equal to 0.1% by weight and less than or equal to 30 % by weight of furfuraldehyde, based on the total weight of the liquid aqueous phase (1).
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the liquid aqueous phase (1) comprises more than or equal to 0.1% by weight and less than or equal to 30 % by weight of one or more organic acids, based on the total weight of the liquid aqueous phase (1).
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the liquid aromatic phase (2) comprises one or more aromatic hydrocarbon compounds having a higher boiling point than furfural.
    [0008]
    8. Process according to any one of claims 1 to 7, characterized in that the ratio of the liquid aqueous phase (1) to the liquid aromatic phase (2) is in the range of 2: 1 to 1: 5.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the process further comprises recovering one or more aromatic hydrocarbon compounds from the liquid organic phase (4) and recycling the compound (s) ) of aromatic hydrocarbon recovered (s) for stage a).
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    同族专利:
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    PL2585184T3|2017-11-30|
    BR112012029213A2|2016-11-29|
    WO2011161141A1|2011-12-29|
    CN102933272A|2013-02-13|
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    US20130232854A1|2013-09-12|
    EP2585184B1|2017-07-26|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-26| B06T| Formal requirements before examination|
    2019-10-15| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-04-07| B09A| Decision: intention to grant|
    2020-11-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10166868.9|2010-06-22|
    EP10166868|2010-06-22|
    PCT/EP2011/060409|WO2011161141A1|2010-06-22|2011-06-22|Process for separating furfural from a liquid aqueous phase comprising furfural and one or more organic acids|
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