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    • 专利摘要:
    method for the production of furfuraldehyde from lignocellulosic biomass material. the present invention provides a method for the production of furfuraldehyde from lignocellulosic biomass material, comprising the steps of: a) contacting the lignocellulosic biomass material with a mixture comprising water and an organic acid at a temperature of at least 100 <198> a pressure of a maximum of 10 bar (absolute) to obtain a first liquid stream comprising hydrolyzed hemicellulose and a second stream comprising lignin and cellulose; b) maintaining the first liquid stream comprising hydrolyzed hemicellulose at a temperature of at least 130 ° c and to obtain a second liquid stream comprising furfural; and c) separating the furfural obtained in step b) from the second liquid stream.
    公开号:BR112012014971B1
    申请号:R112012014971-7
    申请日:2010-12-15
    公开日:2020-09-29
    发明作者:Evert Van Der Heide；Ting Zhang
    申请人:Shell Internationale Research Maatschappij B.V；
    IPC主号:
    专利说明:

    Field of the Invention
    The present invention relates to a method for the production of furfuraldehyde from lignocellulosic biomass material. Background of the Invention
    With the decrease in the supply of crude oil, the use of renewable energy sources is becoming increasingly important as a raw material for the production of hydrocarbon compounds. Biomasses derived from plants and animals are being used to produce liquid and gaseous hydrocarbon compounds. One of the advantages of using biomass is that the CO2 balance is more favorable compared to that of the conventional hydrocarbon supply.
    One of the most commonly used biomass materials is lig-nocellulosic biomass material. Lignocellulosic biomass materials mainly consist of cellulose, 15 hemicellulose and lignin joined together in a complex gel structure, together with optional small amounts of extracts, pectins, proteins and / or ashes.
    Cellulose and hemicellulose, when hydrolyzed to sugars, can also be converted into ethanol and other useful and intermediate products, for example, through microbiological fermentation technologies or through thermochemical conversions, such as aqueous reform phase. In addition, the hemicellulose present in the lignocellulosic biomass material can be processed to obtain sugars, which can later be converted to fuels and chemicals, such as furfuraldehydes. Furfural has several applications in the chemical and petrochemical industry and furfural derivatives are also useful as polymers and resins.
    Several problems associated with furfural production arise due to the complex chemical structure of the lignocellulosic biomass material. The separation of hemicellulose from other lignocellulosic constituents is complicated by the fact that lignin can be lintered and linked in various ways with cellulose and hemicellulose. The pretreatment of the lignocellulosic biomass material makes the individual components more accessible for processing, thus facilitating the production of furfuralde from hemicellulose. Pre-treatment processes, however, have several disadvantages.
    The use of organic solvents, such as formic acid and acetic acid, in pretreatment procedures has the disadvantage that solvent recovery is a complicated and expensive process step.
    The use of biomass destructuring / decomposition steam, such as "steam blast", "steam cooking", "water pressure cooking", "diluted acid hydrolysis", "liquid pre-treatment in hot water ", and" hydrothermal treatment ", have the disadvantage that they are carried out at higher pressures and can alter the properties of lignocellulosic biomass materials. This can result in the degradation of sugars and the formation of inhibitors.
    EP-346,836 describes a process and equipment for the continuous preparation of 5 2-furaldehyde, cellulose and lignin from lignocellulosic material. The described process requires a lignocellulosic material with a reduced particle size, in the range of about 2 to about 10 mm. This lignocellulosic material is first increased by volume at 70 to 90 ° C, after which part of the water is drained. The remaining suspension of the lignocellulosic material in water is hydrolyzed in a first hydrolysis step at 115 to 135 ° C, 10 after which part of the liquid is drained again. Then, the remaining suspension of the lignocellulosic material in water is hydrolyzed in a second two-stage hydrolysis step from 160 ° C to 180 ° C and 200 ° C to 235 ° C, respectively, after which part of the liquid is again drained. The latter liquid also contains 2-furaldehyde. A disadvantage of the process as described in EP-346,836 is the many steps and the large amount of volumes, energy and necessary equipment.
    In pretreatment processes with organic solvents a solvent mixture of lignin extraction is used to extract lignin in high temperature and high pressure digesters. Examples of such pretreatment processes with organic solvents can be found in WO200686861, WO200751269 US20070259412 and USA 2008/0299628. However, pretreatments with organic solvents are also characterized by high capital costs, high energy requirements and solvent recovery problems and less pretreatment efficiency.
    Thus, these pretreatment processes share one or more of the disadvantages that include strict pretreatment conditions, high capital costs, high energy requirements and solvent recovery problems and less pretreatment efficiency.
    It would therefore be an advance in the technique if it were possible to provide an effective and simple method for the pre-treatment of the lignocellulosic biomass material and the subsequent production of furfural. Summary of the Invention
    An effective and simple method for pretreating lignocellulosic biomass material and the subsequent production of furfural has now been discovered.
    Accordingly, the present invention provides a method for the production of furfuraldehyde from lignocellulosic biomass material, comprising the steps of: (a) contacting the lignocellulosic biomass material with a mixture comprising water and an organic acid at a temperature of at least 100 ° C and a pressure not exceeding | 1 MPa (10 bar) (absolute) to obtain a first liquid stream comprising hydro-lysed hemicellulose and a second stream comprising lignin and cellulose; (b) maintaining the first liquid stream comprising the hydrolyzed hemicellulose at a temperature of at least 130 ° C to obtain a second liquid stream comprising furfural, and (c) separating the furfural obtained in step b) from the second liquid stream.
    The method according to the invention allows the lignocellulosic biomass material to be used efficiently for the production of furfural after it has been pre-treated. Advantageously, the method according to the invention makes it possible to carry out the complete process while using the same catalyst (s) at all stages. In addition, the method according to the invention avoids the need to reheat any liquid stream in step b) and makes efficient use of the heat applied in step a).
    In addition, the method according to the invention advantageously allows to use a high solids content and still allows weight ratios of solid to solvent in the range of 1: 3 to 1: 5 to be used.
    Furthermore, the method according to the invention advantageously allows to carry out the process in a reactor. Brief Description of Drawings
    Figure 1 shows a schematic diagram of the method according to the invention. Detailed Description
    In step (a) of the method according to the invention the lignocellulosic biomass material is contacted with a mixture comprising water and an organic acid at a temperature of at least 100 ° C and a pressure not exceeding 1 MPa (10 bar) (absolute) to obtain a first liquid stream comprising hydrolyzed hemicellulose and a second stream comprising lignin and cellulose.
    By a lignocellulosic biomass material, here is meant a material containing 25 lignocellulose obtained directly or indirectly from a biological source, it is preferably understood to be a lignocellulosic material obtained from natural sources.
    Examples of lignocellulosic biomass material include any biological materials containing lignocellulose, such as agricultural waste, forest waste, wood chips, straw, straw, grains, grasses, corn, corn straw, weeds, aquatic plants and / or hay; and / or any material containing biological lignocellulose, such as some municipal waste or household waste.
    Any lignocellulosic biomass material known to be suitable for hydrolysis by those ordinarily skilled in the art can be used in the method according to the present invention. The method of the invention is particularly suitable for the conversion of non-wood lignocellulosic biomass material, particularly lignocellulosic biomass material derived from grasses. Typical grasses include wheat straw, but also miscellaneous, sweet sorghum and bamboo.
    Lignocellulosic biomass material typically includes hemicellulose, lignin and cellulose. In the method according to the invention, it is especially preferred to process the hemicellulose present in the lignocellulosic biomass material to produce furfural.
    The hemicellulose preferably comprises one or more amorphous polymers of 5 sugars of five and six carbons. The lignocellulosic biomass material in the method according to the invention can include, for example, hemicelluloses in an amount of 10% w to 50% w, more preferably in an amount of 20% w to 30% w.
    Lignin preferably comprises a highly cross-linked polymer of phenolic compounds. The lignocellulosic biomass material in the method according to the invention can include, for example, lignin in an amount of 1% w to 40% w; more preferably in an amount of 5 wt% to 30 wt%.
    The cellulose preferably comprises a highly crystalline cellulose polymer, a glucose dimer The lignocellulosic biomass material in the method according to the invention can include, for example, cellulose in an amount of 10% to 50% w, more preferably 15 in an amount between 30% p and 40% p.
    Without wishing to be limited by any type of theory, it is believed that cellulose, hemicellulose and lignin are united in a complex gel structure, together with small amounts of extractive options, pectins, proteins and / or ashes.
    Cellulose and hemicellulose, when hydrolyzed to their sugars, can be converted into ethanol or other useful compounds using any type of fermentation technology known to those usually skilled in the art to be suitable for this purpose. These sugars can also advantageously form the raw material for the production of a variety of chemicals and polymers, either through microbial fermentation or through thermochemical processes such as aqueous phase reforming.
    In a preferred embodiment, the lignocellulosic biomass material is rich in pentosan. By pentosan is meant a type of hemicellulose comprising a polymer of pentose sugars. By a pentose sugar is meant a monosaccharide with five carbon atoms. Examples of preferred pentose sugars include xylose and arabinose. Such pentose sugars can advantageously be converted into furfural.
    Preferably, the lignocellulosic biomass material in the method of the invention comprises equal to or more than 1% by weight of pentosans, more preferably equal to or more than 3% by weight of pentosans, even more preferably equal to or more than 5% by weight pentosans more preferably equal to or more than 10% by weight pentosans. Although there is no upper limit, for practical purposes, the lignocellulosic biomass material used as a feed in the process of the invention can comprise equal to or less than 90% by weight pentosan, preferably equal to or less than 60% by weight, pentosan more preferably equal to or less than 40% by weight pentosan and more preferably equal to or less than 35% by weight pentosan.
    In a preferred embodiment, lignocellulosic biomass comprises particles with an average weight length (which is the largest particle diameter), preferably in the range equal to or more than 0.5 millimeters, more preferably equal to or more than 1 millimeter at 5 meters. equal to or less than 5 centimeters, more preferably equal to or less than 2.5 centimeters, and preferably an average thickness or average thickness component of weight (which is the shortest particle diameter) in the range of equal to or more than 0, 01 millimeters, more preferably equal to or more than 0.1 millimeters, equal to or less than 2.5 centimeters, more preferably equal to or less than 1 centimeter, more preferably 10 equal to or less than 0.2 centimeters.
    If necessary, the particle size of the lignocellulosic biomass material can be reduced prior to its use in contacting step a). Such a particle size reduction can be achieved in any way known to those usually skilled in the art and suitable for that purpose. Suitable methods for reducing particle size include crushing, crushing, grinding, perforating, granulating, shredding and / or any combination of these.
    The lignocellulosic biomass material is subjected to a high temperature and pressure, in the presence of water and an organic acid to hydrolyze hemicellulose. That is, the lignocellulosic biomass material is contacted with the mixture comprising water and organic acid at a temperature of at least 100 ° C and a pressure not exceeding 1 MPa (10 bar) to hydrolyze at least part of the hemicellulose comprised in the material of lignocellulosic biomass such that hydrolyzed hemicellulose is obtained.
    The weight ratio of lignocellulosic biomass material for mixing (i.e., the weight ratio of solid to solvent) is preferably in the range of from 25: 2: 1 to 1:10, more preferably in the range of (1: 3 to 1: 8, more preferably in the range of 1: 3 to 1: 5.
    The organic acid in the mixture comprising water and organic acid is preferably formic acid, acetic acid, citric acid and / or oxalic acid. Without wishing to be limited by any type of theory, it is believed that organic acid can serve the purpose of a catalyst, thus helping in the hydrolysis of hemicellulose and also helping in the destructuring (decomposition) of lignin.
    In step a) the weight percentage of the organic acid in the mixture comprising water and organic acid is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 0.1 to 10% by weight, more preferably in the range from 0.1 to 5% by weight.
    The mixture comprising water and an organic acid can preferably further comprise an inorganic acid, preferably hydrochloric acid, sulfuric acid, nitric acid and / or phosphoric acid.
    Step a) of the method of the invention is preferably carried out in a temperature range of 100 to 220 ° C, more preferably in the range of 130 to 180 ° C.
    Step a) of the method of the invention is preferably carried out at a pressure, where the water at the temperature does not yet reach a boil. For practical purposes, the pressure is preferably in the range of 1 MPa (1 bar absolute) at or above 1.5 MPa (15 bar (absolute)), more preferably at a maximum pressure of 1 MPa (10 bar (absolute)).
    Step a) can be carried out on any type of reactor known to the qualified person to be suitable for that purpose. The reactor is preferably a ballast reactor, a CSTR reactor or a mud reactor having an arrangement for mechanically moving the lignocellulosic biomass. In a preferred embodiment, the reactor contains a lignocellulosic biomass material and in operation a mixture of water and organic acid is sprayed on the lignocellulosic biomass material.
    The lignocellulosic biomass material is preferably in contact with water and the mixture comprising organic acid, for a period of time in the range of 0.1 to 10 hours, preferably in the range of 0.3 to 5 hours, and more preferably 0 , 4 to 2 hours.
    The organic acid and the remaining water mixture at the end of step a) is preferably processed for recycling the organic acid which is preferably carried out by methods such as pressure swing distillation, extraction or extractive distillation. Recycling of organic acid is especially preferred when organic acid is formic acid.
    In step a) a first liquid stream comprising hydrolyzed hemicellulose and a second stream comprising lignin and cellulose are obtained.
    The first liquid stream preferably comprises monomeric sugars, preferably of xylose, water and dilute acid.
    Preferably, the first liquid stream comprises an aqueous solution containing xylose equal to or more than 0.5% by weight of xylose, more preferably equal to or more than 2% by weight of xylose and more preferably equal to or more than 5% by weight of xylose. For practical purposes, the first liquid stream may preferably contain less than or equal to 50% by weight of xylose, more preferably less than or equal to 30% by weight of xylose and more preferably less than or equal to 20% by weight of xylose, with the remainder preferably containing water.
    The second stream preferably comprises cellulose and unstructured lignin.
    The two streams formed in step a) can be separated using separation techniques known to those usually skilled in the art and suitable for this purpose. Preferably, the separation involves removing the liquid from a stream of solids, by removing the liquid from the slurry by pressing, resulting in the formation of two separate streams; a stream of solids and a liquid stream.
    The separation of the first liquid stream comprising hydrolyzed hemicellulose 5 and the second stream comprising lignin and cellulose can be carried out, for example, by a screw press. In a preferred embodiment, the contact in step a) and the separation are carried out simultaneously.
    The lignin and cellulose present in the lignocellulosic biomass material after the separation of the hydrolyzed hemicellulose can preferably be subjected to further processing to obtain lignin and cellulose in purer forms, which can be used for the production of chemicals and fuels.
    In another embodiment, at least part of the first liquid stream obtained comprising hydrolyzed hemicellulose is recycled and contacted with the fresh lignocellulosic biomass material in step a). This advantageously allows the highest concentrations of hydrolyzed hemicellulose (in particular xylose) to be accumulated in the liquid stream.
    In step (b) of the method according to the invention, the first liquid stream comprising hydrolyzed hemicellulose is maintained at a temperature of at least 130 ° C to obtain a second liquid stream comprising furfural.
    Furfural as mentioned in the present invention is an organic compound that is chemically an aromatic aldehyde with a chemical formula of C5H4O2. In its pure state, furfural is a colorless oily liquid, but after exposure to air it quickly turns yellow. Furfural has several applications. Furfural can be used as a solvent in petrochemical refining to extract dienes that can be used to make synthetic rubber from other hydrocarbons.
    Furfural, as well as its furfuryl alcohol derivative, can be used either individually or together with phenol, acetone or urea to produce solid resins. Such resins can be used in the manufacture of fiberglass brakes, aircraft components, automobile brakes. Furthermore furfural can be used as a chemical intermediate in the production of solvents furan and tetrahydrofuran.
    Step b) can be carried out in any type of reactor known to those usually skilled in the art and suitable for this purpose. The reactor may be an autoclave, but is preferably a piston flow reactor, a discontinued reactor or a CSTR reactor (a continuously agitated tank reactor). In a preferred embodiment, step 35 a) and step b) are carried out in sequence in a reactor. This method advantageously reduces capital costs. In another preferred embodiment, step b) is carried out in a reactor aligned in sequence to a reactor where step a) is carried out.
    Step b) is preferably carried out in the presence of a catalyst, preferably an acid catalyst. More preferably, step b) is carried out in the presence of an inorganic acid catalyst. The acid catalyst preferably comprises hydrochloric acid, sulfuric acid, nitric acid and / or phosphoric acid. The acid catalyst used in the present invention is most preferably sulfuric acid since it is readily available and inexpensive to use.
    In an especially preferred embodiment, the first liquid stream obtained from step a) is introduced into step b) in the reactor together with a catalyst, which is preferably an acid catalyst.
    In one embodiment, the acid catalyst is an inorganic acid that is already added in step a) through a mixture comprising water, an organic acid and an inorganic acid.
    In another embodiment, the acid catalyst is an inorganic acid that is added in step b), and at least part of the second liquid stream obtained as a product 15 in step b) (second liquid stream including such inorganic acid) is recycled to step a).
    In yet another embodiment, the acid catalyst is an inorganic acid that is added in step b), separated from the second liquid stream obtained as a product in step b) and recycled to step a).
    As indicated above, advantageously the method according to the invention makes it possible to carry out the complete process at the same time as using the same catalyst at all stages.
    The temperature in step b) is preferably in the range of 130 ° C to 300 ° C, more preferably in the range of 130 ° C to 250 ° C. As indicated above, the method according to the invention advantageously allows to continue heating a first liquid stream comprising hydrolyzed hemicellulose having a temperature of at least 100 ° C (as obtained from step a)) at a temperature of at least 130 ° C (in step b)) essentially without any intermittent cooling.
    Preferably, step b) is carried out for an average time of between 0.5 minutes and 30 120 minutes to obtain the second liquid stream. More preferably, step b) is carried out for a period of time equal to or more than 30 minutes or possibly 60 minutes to produce furfural.
    The second liquid stream comprising furfural preferably contains equal to or more than 1% by weight of furfural, more preferably equal to or more than 3% by weight of furfural and more preferably equal to or more than 5% by weight of furfural and, preferably equal to or less than 20% by weight of furfural, more preferably equal to or less than 15% by weight of furfural, more preferably equal to or less than 10% by weight of furfural. The maximum molar yield of furfural is preferably not less than 50%, more preferably not less than 60%, even more preferably not less than 70%, based on moles of C5 sugars in the first liquid stream comprising hydrolyzed hemicellulose.
    In step c) of the method of the invention, the furfural obtained in step b) is separated from the second liquid stream. The separation step is preferably carried out by means of processes such as solvent extraction, gas extraction, for example, mixture air, and / or vapor end. More preferably, step c) is carried out by at least one extraction, distillation and / or extractive distillation.
    Without wishing to be limited by any kind of theory, it is believed that the steam extraction process can preferably be based on the spontaneous vaporization of furfu-ral, due to changes in the temperature and pressure conditions that are induced in the reactor. More preferably, furfural is removed by extraction, distillation, with a suitable solvent, and / or extractive distillation. Suitable solvents for extraction include, for example, hydrocarbon solvents, such as aromatic solvents or paraffinic solvents, and phosphine oxide solvents, such as tetraoctyl phosphine oxide, and mixtures thereof.
    Without wishing to be limited by any type of theory, it is believed that the change in physico-chemical conditions results in the desorption of furfural and the vaporization of the remaining 20 components of the product stream. Subsequently, the furfural is preferably separated by a cyclone unit and is collected.
    Preferably still, an exhausted aqueous solution remains in step c) after the furfural is separated from the second liquid stream. This depleted aqueous solution preferably comprises a part of water, the organic acid and optionally any unused acid catalyst.
    In a preferred embodiment of the present invention, the second stream of lignin comprising the cellulose obtained in step a) can preferably be subjected to a first water wash step to remove the remaining hemicellulose. The remainder are preferably still mixed with the first liquid stream comprising hydrolyzed hemicellulose to be subjected to step b).
    In another preferred embodiment, the second stream comprising lignin and cellulose is subjected to a washing step with water and an alcohol, such as ethanol.
    Preferably, this washing step is carried out as a second washing step following the aforementioned first washing step, but the second washing step 35 can also be carried out in the absence of the first washing step. The purpose of the second washing step is to separate the lignin and the cellulose. During the second washing step, the second stream is preferably washed with alcohol and water, at a temperature in the range of 40 to 100 ° C and a pressure below 0.4 MPa (4 bar (absolute)), preferably »A pressure in the range of 0.2 to 0.4 MPa (2 to 4 bar (absolute)). Without wishing to be limited by any kind of theory, it is believed that mildly high temperatures help dissolve the .lignin in the alcohol-water mixture. The temperature is preferably optimized at 50 ° C, as a higher temperature can lead to evaporation of the alcohol and a lower temperature can be. less effective in helping dissolve lignin. The residence time of the second stream in the second washing step is preferably 60 minutes. The alcohol used in the second washing step preferably has less than about 4 carbon atoms so that it can be miscible with water.
    Preferably, an alcohol with the carbon chain length from C1 to C3 is used. The ratio of ethanol to water used in the second washing step preferably ranges from 1:10 to 10: 1. At the end of the second stage of. washing, a third liquid stream comprising lignin is obtained. Lignin can be partially dissolved in the mixture of alcohol and water.
    After the aforementioned second washing step, cellulose is preferably the only component left as a solid, preferably in the form of an undissolved cake. This second cellulose-containing solid stream, which is obtained in the second washing step, is preferably essentially free of lignin reprecipitates because the lignin and other dissolved materials preferably remain in solution at all temperatures of the second wash. Thus, preferably a second stream of solids comprising undissolved cellulose and a third liquid stream comprising lignin, constitute the product streams of the second washing step. ;
    Preferably, the lignin and cellulose that are obtained from a second wash can be further subjected to a filtration step, preferably using a filter press. Such a step.filtration is preferably aided by vacuum to accelerate the process. The second stream of solids comprising cellulose can be retained on the filter screen and the third liquid stream comprising lignin can be collected as a filtrate in the tank. This cellulose can preferably be dried before undergoing further processing.
    The third liquid stream comprising a. lignin obtained as the filtrate after cellulose separation can then be further processed to recover lignin. The cellulose and lignin thus obtained can preferably undergo further processing before being supplied for commercial use. ’
    In general, a solid product rich in cellulose obtained by the process already mentioned can be used in industrial applications directly, with or without drying, or subjected to further processing or to modify the cellulose or to convert it to glucose. The cellulose-rich solid product can preferably be processed into paper products using any convenient methods, such as those disclosed in Macdonald, Papermaking and Paperboard Making, vol. 3, TS 1048. J66, 1969. The cellulose-rich solid product can also be useful as fluff pulp, which is generally used in absorbent applications such as diapers and disposable wipes. Cellulose recovered from the solid phase is particularly suitable for the manufacture of dissolving pulp (also known as .quadrature.-cellulose), when its purity is 85% by weight or more. In some cases, cellulose of this purity level is obtained simply by washing and drying the separated solid phase. If necessary, the recovered cellulose can be further purified using various techniques, such as bleaching.
    Cellulose having a purity of 95% wt or more can be obtained in this way. The cellulose obtained in the process of the invention in most cases is easily and quickly hydrolyzed to glucose and soluble glucose oligomers. The presence of lignin on the surface of the cellulose fibers is considered to prevent the enzymatic hydrolysis of cellulose for the formation of sugars. Lignin is believed to form a physical barrier to water, thus inducing hydrolysis to proceed slowly. In the method according to the invention as described above, efficient removal of lignin exposes more cellulose to the fiber surface, allowing better contact with water (and added enzymes or another catalyst), and therefore increases the reaction rate . Cellulose can be catalytically or thermally converted to various organic acids, alcohols and other materials.
    The lignin produced in accordance with the invention is of high purity, is essentially free of sulfur and other chemicals and can preferably be used as a fuel. As a solid fuel, lignin is similar to carbon in energy content. Lignin can act as an oxygenated component in liquid fuels to increase octane while meeting standards as a renewable fuel. The lignin produced here can preferably be used as a chemical precursor to produce lignin derivatives. Lignin can preferably be mixed with up to 20% formaldehyde and therefore can be used in the preparation of polyphenolic polymers such as Bakelite. Detailed Description of the Figure
    The method according to the present invention is exemplified below, together with the flowchart shown in Figure 1.
    As shown, the process of Figure 1 includes a step a), here also referred to as the cooking step (102), in which the lignocellulosic biomass material is cooked at an elevated temperature in the presence of a mixture comprising water and an organic acid. . Preferences for this step are as described above for step a). In this step (102), a part of the hemicellulose is illustrated to be hydrolyzed to monomeric sugars. In Figure 1 the sugars formed are mainly C5 sugars such as xylose. In addition, lignin, which is present in lignocellulosic biomass material, is unstructured without being removed.
    The cooking step (102) results in the formation of two streams: a first stream comprising hemicellulose hydrolyzate (monomeric sugars), preferably 5 of xylose, water and dilute acid solution, and a second stream comprising cellulose and unstructured lignin. The organic acid and the aqueous mixture remaining at the end of the cooking step (102) is preferably processed for recycling the organic acid (not explicitly illustrated in Figure 1). The recovery of the organic acid and the aqueous mixture is preferably carried out as previously described for step a) by methods such as pressure oscillation, extraction or extractive distillation.
    The two streams formed as a result of the cooking step can be separated using separation techniques, as described here above for step a), such as for example a screw press. As shown in Figure 1, the cooking step (102) and the separation step are preferably carried out simultaneously.
    The first stream obtained in step (102) as mentioned above is rich in sugars. In Figure 1, the first stream obtained is then subjected to a heat treatment step (104) (illustrative for step b)) for the production of a product stream comprising furfural. Preferences for this step are as described above in step b). In the preferred embodiment of Figure 1, the first liquid stream is introduced into the reactor together with a catalyst, which is preferably an acid catalyst, the most preferably the sulfuric acid. The product stream obtained as a result of step (104) primarily comprises furfural. The maximum molar yield of furfural is preferably not less than 50%, more preferably not less than 60%, even more preferably not less than 70%.
    The heat treatment step (104) in Figure 1 is preferably followed by a separation step (106) (illustrative for step c)), in order to obtain furfural from the product stream of the heat treatment step ( 104). Preferences for the separation step (106) are as described above for step c).
    The furfural obtained can be derived to form furfuryl alcohol or other industrially applicable furfural derivative which are also within the scope of the invention (not shown in Figure 1).
    As illustrated in the preferred embodiment of fig. 1, an exhausted aqueous solution remains after the furfural is separated from the product stream. This depleted aqueous solution preferably comprises a part of water, the organic acid (formic acid) and unused acid catalyst.
    In the preferred embodiment of Figure 1, the second stream formed at the end of the separation step, for example, in the screw press, is subjected to a water washing step (108) to remove the remains of hemicellulose. The remainder are even more preferably mixed with the first stream and are thus subjected to the heat treatment step (104) to form the furfural.
    The second stream comprising lignin and cellulose is even more preferably subjected to a second washing step (not shown in Figure 1) in the presence of water and ethanol. Preferences for this second washing step are as described above.
    The process according to the invention is further illustrated by means of the following non-limiting examples. Example 1: Hydrolysis of birch wood chips
    Birch sawdust was contacted with a 1% by weight aqueous formic acid solution in a birch wood weight ratio to the 1 to 9.57 aqueous solution at about 155 ° C and 0.5 MPa ( 5 bar) in a 300 cmJ autoclave for 240 minutes in order to hydrolyze lignocellulose in birch wood chips.
    The results are illustrated in Table 1 below. As illustrated by the total xylose yield recovered in Table 1, xylose was obtained in yields of up to about 7 wt%. The mixture of xylose and furfural obtained may be less suitable for fermentation due to the presence of furfural, but it is an excellent starting point for the subsequent production of furfural. Example 2: Bagasse hydrolysis
    Bagasse was contacted with a 1% w aqueous formic acid solution in a bagasse weight ratio for the 1:10 aqueous solution at about 155 ° C and 0.5 MPa (5 bar) in a 300 autoclave cm3 for 3 hours in order to hydrolyze the lignocellulose contained in the bagasse. Then the contents of the autoclave were filtered. The filtrate was recycled for a second round to hydrolyze a second fresh batch of bagasse and the filtrate obtained from the second round was recycled for a third round to hydrolyze a third batch of bagasse. The residues after each filtration were washed with fresh water (in a 1:10 ratio of bagasse and water by weight). The results are shown in tables 2a and 2b below. As illustrated, by recycling the filtrate, xylose yields (not including furfural yield) of more than 3% w can be easily obtained. As further illustrated, acetic acid is also removed, making residual cellulose very suitable for fermentation purposes. Example 3: Furfural production
    A 5% w aqueous solution of xylose (representative for a hydrolyzed hemicellulose stream) with 1% w formic acid or 0.5% w sulfuric acid is introduced into a piston flow reactor and an autoclave, respectively , at 220 ~ 230 ° C and 3 MPa (30 bar). The results are shown in tables 3, 4, 5 and 6 below:
    Table 1: Hydrolysis of birch sawdust
    *** The total recovered xylose yield was determined by calculating the theoretical amount of xyose required for the formation of the measured furfural yield and adding that theoretical amount of xylose to the measured xylose yield in column 5. ** Percentages of yield are determined in solution and calculated based on the initial weight of the birch wood chips. * Mean ± deviation as determined in samples taken in pairs. HMF = hydroxymethylfurfural
    Table 2a: Bagasse Hydrolysis

    Table 2b Bagasse Hydrolysis
    1: calculated based on the input of fresh biomass
    Table 3 - Production of Furfural in a piston flow reactor with 1% p formic acid
    Test conditions: water, 230 ° C, 3 MPa (30 bar),% p formic acid, 5% p xylose, piston flow reactor.
    Table 4 - Production of Furfural in a piston flow reactor with 0.5% p of sulfuric acid
    Test conditions: water, 230 ° C, 30 bar, 0.5% w H2SO4, 5% w xylose, piston flow reactor.
    Table 5 - Production of furfural in an autoclave with 1% p formic acid
    Test conditions: water, 230 ° C, 30 bar, 1% p formic acid, 5% p xylose, autoclave
    Table 6: Production of Furfural in an autoclave with 0.5% w of sulfuric acid

    Experiment conditions: water 220 ° C, 25.5 bar, 0.5% p H2SO4, 5% p xylose, autoclave.
    权利要求:
    Claims (11)
    [0001]
    1. Method for the production of furfuralde from lignocellulosic biomass material, CHARACTERIZED by the fact that it comprises the steps of: a) contacting the lignocellulosic biomass material with a mixture comprising water and an organic acid at a temperature at least 100 ° C and a maximum pressure of 1 MPa (10 bar) (absolute) to obtain a first liquid stream comprising hydrolyzed hemicellulose and a second stream comprising lignin and cellulose; b) maintaining the first liquid stream comprising hydrolyzed hemicellulose at a temperature of at least 130 ° C to obtain a second liquid stream comprising furfural; and i • c) separate the furfural obtained in step b) from the second liquid stream.
    [0002]
    2. Process, according to claim 1, CHARACTERIZED by the fact that it comprises contacting the second stream obtained in step (a) with water to remove the 15 remains of the hydrolyzed hemicellulose.
    [0003]
    3. Process according to claim 1 or claim 2, CHARACTERIZED by the fact that the organic acid used in step a) is formic acid, acetic acid, citric acid and / or oxalic acid. s
    [0004]
    4. Process according to claim 1, CHARACTERIZED by the fact that the mixture comprising water and an organic acid additionally comprises an inorganic acid, preferably hydrochloric, sulfuric, nitric and / or phosphoric acid.
    [0005]
    5. Process according to any one of claims 1 to 4, CHARACTERIZED by the fact that the amount of organic acid used is 0.1 to 20% by weight.
    [0006]
    6. Process according to any of the preceding claims, CHARACTERIZED by the fact that step b) is carried out in a batch reactor, a piston flow reactor or a continuously agitated tank reactor.
    [0007]
    7. Process according to any one of the preceding claims, CHARACTERIZED by the fact that step b) is carried out in the presence of an additional inorganic acid catalyst.
    [0008]
    8. Process according to claim 7, CHARACTERIZED by the fact that the acid catalyst is hydrochloric, sulfuric, nitric, and / or phosphoric acid.
    [0009]
    9. Process according to claims 1 to 8, CHARACTERIZED by the fact that it additionally comprises adding the inorganic acid catalyst in step b), and recycling at least part of the second liquid stream to step a).
    [0010]
    10. Process, according to any of the preceding claims, CHARACTERIZED by the fact that step b) is carried out for an average time of between 0.5 minutes and 120 minutes to obtain the second liquid stream.
    [0011]
    11. Process, according to claim 1, CHARACTERIZED by the fact that step c) is carried out by means of at least one distillation, extraction and / or extractive distillation.
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    同族专利:
    公开号 | 公开日
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    US20110144359A1|2011-06-16|
    WO2011073253A1|2011-06-23|
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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|
    2019-01-29| B06T| Formal requirements before examination|
    2020-06-09| B09A| Decision: intention to grant|
    2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09179462.8|2009-12-16|
    EP09179462|2009-12-16|
    PCT/EP2010/069750|WO2011073253A1|2009-12-16|2010-12-15|Method for producing furfural from lignocellulosic biomass material|
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