WO2024256571A1 - Procédé de production de furfural - Google Patents

Procédé de production de furfural Download PDF

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Publication number
WO2024256571A1
WO2024256571A1 PCT/EP2024/066427 EP2024066427W WO2024256571A1 WO 2024256571 A1 WO2024256571 A1 WO 2024256571A1 EP 2024066427 W EP2024066427 W EP 2024066427W WO 2024256571 A1 WO2024256571 A1 WO 2024256571A1
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evaporator
evaporated
furfural
downstream
optionally
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Rudy Parton
Aris DE RIJKE
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Gfbiochemicals Ip Assets Bv
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Gfbiochemicals Ip Assets Bv
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions

Definitions

  • This invention relates to a method for producing furfural from a pentose or pentosan-containing starting material.
  • Lignocellulosic biomass materials primarily consist of cellulose, hemicellulose, and lignin bonded together in a complex structure along with optional small quantities of extractives, pectins, proteins, and/or other materials.
  • the pentose sugars in hemicellulose present in the lignocellulosic biomass material can be processed to obtain pentose sugars which can later be converted to fuels and chemicals, such as furfurals.
  • Furfural has various applications in the chemical and petrochemical industry and the derivatives of furfural are also useful as polymers and resins.
  • Furfural also known as furan-2-carboxaldehyde, fural, furfuraldehyde, 2-furaldehyde, or pyromucic aldehyde
  • furfural also known as furan-2-carboxaldehyde, fural, furfuraldehyde, 2-furaldehyde, or pyromucic aldehyde
  • pentoses particularly xylose
  • Pentoses may be obtained from pentosans that are, in turn, obtained from hemicellulose present in lignocellulosic biomass.
  • a multi-effect evaporator can be used to evaporate water.
  • vapour from one body heats a second body at a lower boiling temperature.
  • the first effect is heated directly with steam, and the additional bodies are ordered based on descending boiling temperature (or pressure).
  • Multiple effect evaporation is commonly applied to improve the energy efficiency of evaporation and known by those skilled in the art.
  • W02006095340 discloses a plurality of evaporators connected in series. In each successive evaporator, more water is distilled off. However, no chemical reaction occurs within each evaporator.
  • EP 0124507B1 produces furfural from diluted aqueous solution in a series of reactors, each reactor operating at a different temperature and pressure, while recovering the furfural partially in the condensate.
  • This condensate is formed by flashing of part of the liquid entering a downstream reactor as this downstream reactor is operating at lower temperature and pressure than the upstream reactor.
  • the total amount of vapour produced is limited by the temperature difference between the first and last reactor in the series. As no evaporation takes place in the reactor, the majority of the produced furfural will remain in the liquid phase of the reactors, where it will partially degrade into unwanted by-products.
  • Marcotullio (TU Delft; US 2012/0108829; corresponds with WO2012/057625) concerns producing furfural from pentoses and/or water soluble pentosans.
  • the process comprises converting pentoses and/or water soluble pentosans in aqueous solution, in a first step, to furfural and, in a second step, feeding the aqueous solution containing furfural obtained in the first step to the top of a distillation column to produce an aqueous, liquid downflow, which column is heated at the bottom to produce an upflow water vapour flow, recovering a gaseous water and furfural containing product stream from the top of the column, compressing the vapour flow and condensing it on the hot side of a reboiler at the bottom of the column.
  • aqueous stream containing 2.03 wt% of pentoses is fed to an adiabatic pre-reactor and the resulting mixture containing 0.71 wt% of xylose and 0.87 wt% furfural is fed to a reactive distillation column.
  • a reactive distillation column is not a film evaporator because, in each stage of the distillation column below the feeding line in the liquid phase, the catalyst is present. That means that the vapours, made in each stage below the feeding line, are condensed in the stage above the stage where they are vaporized.
  • the catalyst can catalyse the reaction between the furfural made in the stage below and another furfural, or an intermediate or a side product or the sugars present in the liquid phase of that stage. Those reactions can lead to side products and decrease the selectivity and therefore the yield.
  • the vapours are removed from the liquid which contains the catalyst and, after condensing, they do not come back into contact again with the catalyst dissolved in the reactive liquid.
  • the vapours made are always coming from a liquid phase containing the catalyst in which, continuously, reagents (pentose sugars) are converted to product (furfural) and product (furfural) is removed via vaporisation and is then condensed to a liquid without coming in contact with the catalyst anymore after condensation.
  • WO2015/175840 (TU Delft) describes a kind of co-current bubble column in which the bubbles are the vapour/steam generated in the heat exchanger at the bottom where also the liquid inlet is.
  • the reaction conditions in the bottom are such that, there, the pentose concentration is relatively high and furfural relatively low, so the furfural can do less undesirable reactions and, when the bubbles and liquid travel upwards through the column, the furfural concentration increases and sugar concentration decreases. In that way, according to the authors undesirable side reactions are minimised. See page 5, lines 15-22:
  • the present invention aims to remove directly the furfural made as much as possible. Therefore we propose a film evaporator as reactor.
  • the energy is delivered by the hot surface in contact with the liquid containing catalysts and sugars. So the furfural made is evaporised at the surface and it has to travel only through a thin layer to escape from the reactive environment. Moreover, the vapours will be condensed in the next film evaporator to heat the surface and to evaporate newly fresh made furfural. Because it is only indirectly in contact, the condensed furfural does not come in contact any more with the catalyst and cannot be degraded.
  • US 2,369,655 discloses that the pentose sugars are converted up to high conversion in the gun.
  • the objectives of the method of the present invention are one or more of:
  • a method for producing furfural, from a liquid stream of pentose or pentosan-containing starting material, in an evaporator comprising: providing a film of the liquid stream on heat exchangers of the evaporator, wherein the mean temperature of the liquid stream in the evaporator is at least 170°C; heating the film by indirectly contacting a heated vapour source with the film on the heat exchangers; forming and simultaneously evaporating furfural, thereby separating a non-evaporated liquid fraction comprising an acid catalyst and unreacted pentose or pentosan-containing material, from an evaporated fraction comprising evaporated furfural and preventing the evaporated furfural from further contacting the acid catalyst; wherein the evaporator is a film evaporator.
  • the liquid stream comprises a prehydrolysate.
  • the liquid stream, optionally a prehydrolysate, that is brought into the pressurised continuous flow reactor has a solids contents of between 3 and 20% (w/w), optionally between 4 and 12% (w/w), and further optionally between 5 and 10% (w/).
  • the method reduces unwanted by-products by separating continuously, immediately and continuously, an evaporated fraction comprising evaporated furfural from a liquid stream in an evaporator.
  • the method reduces the energy requirements by indirectly heating a downstream evaporator with the evaporated fraction comprising evaporated furfural from an upstream evaporator.
  • the evaporator may be selected from the group consisting of rising film evaporators, falling film evaporators, wiped/agitated film evaporators and thin film evaporators and is optionally independently selected from the group consisting of rising film evaporators, falling film evaporators, and wiped/agitated film evaporators.
  • the pentose or pentosan-containing starting material comprises at least 0.05 % (w/w) furfural, optionally at least 0.1 % (w/w), further optionally at least 0.2 % (w/w) furfural and, optionally, less than 5 % (w/w) furfural; and I or wherein the liquid stream of pentose or pentosan-containing starting material comprises no more than 20 % (w/w), optionally no more than 15 % (w/w), further optionally no more than 10 % (w/w), xylose.
  • the acid catalyst is selected from the group consisting of hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid (optionally selected from the group consisting of sulphuric acid, nitric acid, and phosphoric acid). Further optionally, the acid catalyst is additionally selected from the group consisting of organic acids such as, but not limited to, formic acid, acetic acid or levulinic acid. Still further optionally, the acid catalyst is selected from the group consisting of mixtures of one or more organic acids with one or more acid catalysts selected from hydrochloric acid, sulphuric acid, nitric acid, and phosphoric acid (optionally sulphuric acid, nitric acid, and phosphoric acid).
  • the acid catalyst is sulphuric acid; and I or when an organic acid is present in the acid catalyst mixture, the organic acid is selected from formic acid, acetic acid or levulinic acid, and mixtures thereof; and I or the acid catalyst is a mixture of sulphuric acid and one or more organic acids selected from formic acid, acetic acid and levulinic acid.
  • the acid catalyst selected from the group consisting of hydrochloric acid, sulphuric acid, nitric acid, and phosphoric acid, is present in an amount of 0.01% to 4% (w/w). While the acid catalyst may additionally comprise one or more organic acids, it is the acid catalyst, selected from the group consisting of hydrochloric acid, sulphuric acid, nitric acid, and phosphoric acid, that is present in an amount of 0.01% to 4% (w/w).
  • the method further comprises means for adding the acid catalyst to the pentose or pentosan-containing starting material upstream of the evaporator.
  • the pentose or pentosan-containing starting material is brought as a liquid stream into the evaporator.
  • at least 20% (w/w), optionally at least 25% (w/w), further optionally at least 30% (w/w), of the liquid stream is evaporated in the evaporator.
  • more than 50% (w/w), optionally more than 70% (w/w) , further optionally more than 90% (w/w), of the pentoses or pentosans in the liquid stream may be converted to furfural and by-products (such as, but not limited to, humins including oligofuranics) in the evaporator.
  • the evaporator comprises a sump and a vapour collector and a non-evaporated liquid fraction is collected in the sump and an evaporated fraction comprising evaporated furfural is collected in the vapour collector; and the liquid stream for the evaporator comprises at least some of the non-evaporated liquid fraction that has been recycled from the same, or another, evaporator.
  • the mean temperature of the liquid stream in the evaporator is at least 190°C, optionally at least 210°C, further optionally at least 230°C.
  • the method is carried out in a series of two or more reaction vessels, at least one of which is an evaporator; and wherein the pentose or pentosan-containing starting material is brought as a liquid stream into the first reaction vessel.
  • the most upstream and I or the second most upstream reaction vessel in the series of reaction vessels is an evaporator; and I or the most downstream reaction vessel in the series of reaction vessels is not an evaporator.
  • each reaction vessel in the series of reaction vessels may be an evaporator.
  • the most downstream reaction vessel may be a forced circulation evaporator and the other reaction vessels of the series of two or more reaction vessels may be selected from rising film evaporators and falling film evaporators; and are optionally falling film evaporators.
  • the at least one evaporator is independently selected from the group consisting of a falling film evaporator or a series of falling film evaporators; a rising film evaporator or a series of rising film evaporators; a wiped/agitated film evaporator or a series of wiped/agitated film evaporators; a thin film evaporator or a series of thin film evaporators; or a mixture of rising film evaporators, falling film evaporators, wiped/agitated film evaporators, and thin film evaporators.
  • the mean temperature of the liquid stream in the evaporator is at least 190°C, optionally at least 210°C, further optionally at least 230°C.
  • the method is carried out in a series of two or more reaction vessels, at least one of which is an evaporator; and wherein the pentose or pentosan-containing starting material is brought as a liquid stream into the first reaction vessel.
  • the mean temperature of the liquid stream in the most upstream reaction vessel in a series of reaction vessels is at least 190°C, further optionally at least 210°C, further optionally at least 230°C.
  • a nonevaporated liquid fraction is collected in a sump; and an evaporated fraction comprising evaporated furfural is collected in a vapour collector; and at least some of the liquid stream, in the at least one evaporator, comprises non-evaporated liquid fraction that has been recycled from the same evaporator; and I or from a more upstream evaporator; and I or from a more downstream evaporator, optionally the most downstream evaporator; and I or wherein at least some of the liquid stream comprises recycled non-evaporated liquid fraction from the same evaporator in each of the one or more evaporators.
  • the two or more reaction vessels are configured as multiple effect reaction vessels.
  • the, or each, evaporator comprises, in use, a heated vapour source for the upstream evaporator is for steam at a temperature that is higher than the mean temperature of the liquid stream in the upstream evaporator and wherein the heated vapour source for the one or more downstream evaporators is for vapour from the evaporated fraction comprising evaporated furfural, from an evaporator that is upstream of the one or more downstream evaporators; wherein the upstream evaporated fraction indirectly heats the liquid stream in the one or more downstream evaporatosr and condenses to produce a furfural condensate; and means for collecting the evaporated fraction comprising furfural condensate from the, or each, downstream evaporator.
  • the evaporated fraction is routed through a mechanical vapour compressor to increase pressure and temperature to such a level that the vapour can be used as heat source for the same evaporator and/or another evaporator.
  • Mechanical vapour recompression is an open heat pump system in which the pressure and temperature of the vapour, together with the corresponding saturation temperature, are increased by means of compression. Mechanical Vapour Recompression is commonly applied in chemical industry and known by those skilled in the art.
  • the residence time of the liquid stream in the, or each, evaporator, including the sump and the vapour collector is less than 10 minutes, optionally less than 5 minutes, further optionally less than 1 minute.
  • the heated vapour source for the most upstream evaporator is for steam at a temperature that is at least 4°C higher, optionally at least 7°C higher, further optionally at least 10°C higher, than the mean temperature of the liquid stream in the most upstream evaporator.
  • the two or more reaction vessels are not configured as multiple effect reaction vessels; and wherein the heated vapour source for each reaction vessel is for steam.
  • the series of two or more reaction vessels is an upstream evaporator, and a downstream evaporator; and wherein the upstream evaporator and the downstream evaporator are configured as multiple effect evaporators.
  • the liquid stream comprises at least some of the non-evaporated liquid fraction that has been recycled from the same evaporator; and I or at least some of the non-evaporated liquid fraction is transferred from the upstream evaporator into the downstream evaporator; and the method comprises indirectly heating the liquid stream in the downstream evaporator with the upstream evaporated fraction comprising evaporated furfural , and condensing the upstream evaporated fraction comprising evaporated furfural to produce a furfural condensate; and separately collecting the non-evaporated liquid fraction and the evaporated fraction comprising furfural in each evaporator.
  • At least 10% (w/w), optionally at least 15% (w/w), further optionally at least 20% (w/w), of the liquid stream is evaporated from each evaporator.
  • more than 10% (w/w), more optionally more than 20% (w/w), more optionally more than 30% (w/w), still more optionally more than 40% (w/w), of the pentoses and pentosans in the liquid stream to each evaporator is converted in each evaporator.
  • the mean temperature of the liquid stream in each evaporator independently falls by about 4°C to 40°C, optionally between about 4°C to 20°C, further optionally between about 4°C to 10°C, between the upstream evaporator and the downstream evaporator.
  • the series of two or more reaction vessels is an upstream evaporator, and a downstream evaporator, and wherein the upstream evaporator and the downstream evaporator are not configured as multiple effect evaporators.
  • the series of two or more reaction vessels is an upstream evaporator, and first and second downstream evaporators; and wherein the evaporators are configured as multiple effect evaporators.
  • the liquid stream comprises at least some of the non-evaporated liquid fraction that has been recycled from the same evaporator; and I or at least some of the non-evaporated liquid fraction from the upstream evaporator is for the first downstream evaporator and at least some of the nonevaporated liquid fraction from the first downstream evaporator is for the second downstream evaporator; and wherein the heated vapour source for the upstream evaporator is for steam, the heated vapour source for the first downstream evaporator is for vapour from the evaporated fraction comprising evaporated furfural from the upstream evaporator and the heated vapour source for the second downstream evaporator is for vapour from the evaporated fraction comprising evaporated furfural from the first downstream evaporator.
  • the upstream evaporator and the first downstream evaporator are falling film evaporators and the second downstream evaporator is a forced circulation evaporator.
  • the series of two or more of reaction vessels is an upstream evaporator, and first and second downstream evaporators; and wherein the evaporators are not configured as multiple effect evaporators.
  • the series of two or more reaction vessels is an upstream evaporator, and first, second and third downstream evaporators; and wherein the evaporators are configured as multiple effect evaporators.
  • the liquid stream comprises at least some of the non-evaporated liquid fraction that has been recycled from the same evaporator; and I or at least some of the non-evaporated liquid fraction from the upstream evaporator is for the first downstream evaporator, at least some of the nonevaporated liquid fraction from the first downstream evaporator is for the second downstream evaporator, and at least some of the non-evaporated liquid fraction from the second downstream evaporator is for the third downstream evaporator; and wherein the heated vapour source for the upstream evaporator is for steam, the heated vapour source for the first downstream evaporator is for the evaporated fraction comprising evaporated furfural from the upstream evaporator, the heated vapour source for the second downstream evaporator is for vapour from the evaporated fraction comprising evaporated furfural from the first downstream evaporator, and the heated vapour source for the third downstream evaporator is for vapour from the evaporated fraction comprising evaporated furfural from the second downstream evaporator.
  • the upstream evaporator and the first and second downstream evaporators are falling film evaporators and the third downstream evaporator is a forced circulation evaporator.
  • the mean temperature of the liquid stream in the upstream evaporator and in the one or more downstream evaporators independently falls by about 4 to 30°C or 40°C, optionally about 4 to 20°C, further optionally about 4 to 15°C, still further optionally between about 4°C to 10°C, between the upstream evaporator and each subsequent downstream evaporator.
  • the series of two or more reaction vessels is an upstream evaporator, and first, second and third downstream evaporators; and wherein the evaporators are not configured as multiple effect evaporators.
  • the evaporated fraction is subjected to mechanical vapour compression and the compressed evaporated fraction is used as a heat source for the same evaporator and/or another evaporator.
  • Figure 2 shows 2 film evaporators in series with heat integration via effect
  • Figure 3 shows 3 film evaporators in series with heat integration via effect
  • Figure 4 shows 4 film evaporators in series with heat integration via effect
  • FIG. 5 shows 1 film evaporator heated with steam Detailed Description of the Invention
  • lignocellulosic biomass material examples include any lignocellulose containing biological materials, such as agriculture waste, forest residue, wood chips, straw, chaff, grain, grasses, corn, cornhusks, weeds, aquatic plants and/or hay; and/or any lignocellulose containing material of biological origin, such as some municipal waste or household waste.
  • the lignocellulosic biomass material typically includes hemicellulose, lignin and cellulose.
  • the hemicellulose present in the lignocellulosic biomass material is processed to produce furfural.
  • the hemicellulose containing liquid stream may contain organic acids such as formic acid, acetic acid or levulinic acid. These acids can also ‘autohydrolyse’ the pentose sugars to furfural under suitable reaction conditions.
  • organic acids such as formic acid, acetic acid or levulinic acid.
  • These acids can also ‘autohydrolyse’ the pentose sugars to furfural under suitable reaction conditions.
  • the weak acidity of organic acids compared to sulfuric acid suggests that either higher temperatures, higher residence times and/or higher acid concentrations may be needed.
  • invention or “present invention is a non-limiting term and is not intended to refer to any single variation of the particular invention but encompasses all possible variations described in the specification and recited in the claims.
  • the term “about” modifying the quantity of an ingredient or reactant of the invention employed refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about’, the claims include equivalents to the quantities.
  • the term “about” may mean within 10% of the reported numerical value, preferably within 5% of the reported numerical value.
  • Conversion percentages from the pentoses and pentosans in the pentose or pentosan-containing starting material, are calculated on a molar basis.
  • the methods of the invention re carried out under autogenic pressure.
  • Rising Film Evaporator In this type of evaporator, the vapour formed moves upwards and drags the liquid film, which continues to boil and generate more vapour. It gives excellent heat transfer performance and is generally inexpensive to manufacture. However, it has a higher pressure drop through the tubes compared to a falling-film evaporator and has a higher liquid hold-up.
  • Falling Film Evaporator In this type of evaporator, the liquid stream is introduced at the upper end of the vertical tubes, and the film travels downwards by gravity, assisted by vapour drag. It has the inherent advantage of being a downflow device and produces thinner films and shorter residence times than a rising film evaporator. However, it is crucial, with falling film evaporators, to have a good distribution of the liquid stream uniformly to every tube and around the circumference of each tube.
  • Wiped / Agitated Thin Film Evaporators are equipped with wipers to distribute a thin liquid film uniformly across the heat transfer surface and have again shorter residence times than falling film evaporators.
  • Short-Tube Vertical Evaporator It is still widely used in the industry, and circulation past the heating surface is induced by boiling in the tubes.
  • the body is a vertical cylinder, usually of cast iron, and the tubes are expanded into horizontal tube sheets that span the body diameter. It has high heat-transfer coefficients at high temperature differences and is relatively inexpensive. However, it has poor heat transfer at low temperature differences and a high holdup that results in higher residence times and increased conversion to undesired by-products.
  • Horizontal-Tube Evaporator In these types, hot medium is inside, and the mixture is outside of the tubes. It has a very low headroom and a large vapour-liquid disengaging area, but it is relatively expensive and has difficulties in maintaining proper liquid distribution and proper wetting of the surface.
  • Short Path Evaporators These types of evaporators would be able to perform the task of evaporation, with proper residence time control, similar to FFE and RFE. However, the low furfural- concentrations in combination with the ease of evaporation makes these types of capital-intensive evaporators too expensive for this role.
  • Falling film evaporators (FFE) with recycle are suggested for use herein due to their good heat transfer coefficients and ability to maintain adequate residence time.
  • Evaporators are usually 1 , 3 or 6 m in length. If a longer residence time is desired, either a longer evaporator is chosen and I or the liquid stream from an evaporator may be recycled back into the same evaporator.
  • evaporator where 1 evaporator is employed, more than 50%, optionally more than 70%, further optionally more than 90%, of the pentoses or pentosans in the liquid stream are converted to furfural and byproducts in the evaporator.
  • the % conversion in each reaction vessel may be modified by maintaining the higher reaction temperature; using a higher acid concentration; using a longer residence time by either making the tubes longer (not practical) or by recycling to the same evaporator; and I or by including more tubes in each evaporator.
  • At least 20%, optionally at least 25%, further optionally at least 30%, of the liquid stream is evaporated from the evaporator.
  • At least 15%- 40%, optionally at least 20%, further optionally at least 25%, still further optionally at least 30%, of the liquid stream is evaporated from the upstream evaporator.
  • the volume is progressively reduced and it’s the energy efficiency of the heat transfer from the furfural-containing vapour that determines the evaporation rate in each subsequent downstream evaporator.
  • Example 1 3 film evaporators in series all at the same temperature heated with steam
  • a synthetic aqueous prehydrolysate (11) containing xylose is optionally preheated and is mixed with acid catalyst (optionally sulfuric acid) up to the appropriate acid concentration and brought into the film evaporator 1 .
  • acid catalyst optionally sulfuric acid
  • the film evaporator 1 is heated via indirect heat exchange with steam (15) up to a temperature above 170°C.
  • the condensate of the steam leaves the film evaporator 1 via pipe 16.
  • the total residence time, including optional partial recycle, over the first film evaporator 1 was sufficient to reach a desired conversion.
  • Concentrate 1 enters the second film evaporator 2 at a similar temperature as in the first film evaporator 1 and is heated via indirect heat exchange with steam (25) at a temperature similar to that of the first film evaporator 1 .
  • the condensate of the steam leaves the second film evaporator 2 via pipe (26).
  • the total residence time, including optional partial recycle, over the second film evaporator 2 was sufficient to reach a desired conversion of the xylose.
  • part of the water and furfural is evaporated (for example, between 15% and 35% of the total liquid stream entering the second film evaporator 2) and the vapors are enriched in furfural compared to the liquid phase.
  • These vapors leave the second film evaporator 2 via pipe (23).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the second film evaporator 2 via pipe (22) and is called concentrate 2.
  • Concentrate 2 enters the third film evaporator 3 at a similar temperature to that of the second film evaporator 2 and is heated via indirect heat exchange with steam (35) at a temperature similar to that of the second film evaporator 2.
  • the condensate of the steam leaves the third film evaporator 3 via pipe (36).
  • the total residence time, including optional partial recycle, over the third film evaporator 3 was sufficient to reach a desired conversion of the xylose.
  • part of the water and furfural is evaporated (for example, between 15% and 35% of the total liquid stream entering the third form evaporator 3) and the vapors are enriched in furfural compared to the liquid phase. These vapors leave the third film evaporator 3 via pipe (33).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the third film evaporator 3 via pipe (32) and is called concentrate 3.
  • the vapors containing furfural optionally can be combined and condensed with (50) cooling water or with another stream which can be heated or can be used for heating a distillation column or the heat can be integrated in another manner, optionally via (47) to pre-heat the prehydrolysate.
  • the condensed furfural can be further separated and purified in a conventional furfural distillation and purification.
  • Concentrate 3 can be recycled to the first film evaporator 1 . In that case, a purge is needed to avoid blowing up the reaction section with heavies, optionally salts.
  • the concentrate 3 can also be recycled to the pretreatment. It can be neutralized and the furfural can be recovered and it can also be sent to the waste water treatment. In all 3 previous cases, at least part of the furfural will be recovered in addition, but in most cases it will require extra energy.
  • part of the water and furfural is evaporated (at least 10%; most optionally at least 40% of the total liquid stream entering the first film evaporator 1) and the vapors are enriched in furfural compared to the liquid phase. These vapors leave the film evaporator via pipe (13).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the film evaporator via pipe (12) and is called concentrate 1 .
  • Concentrate 1 can be optionally flashed in a flash vessel to the temperature which is between 4 and 40°C below the temperature of the first film evaporator 1 and, after that, enters film evaporator 2 via pipe (12).
  • the second film evaporator 2 operates at a temperature between 4 and 40°C below the temperature of first film evaporator 1 and is indirectly heated with the furfural containing vapors (13) of first film evaporator 1 .
  • the condensate of those furfural containing vapors leaves the second film evaporator 2 via pipe (17).
  • the residence time including optional recycle, is at a temperature, and higher acid concentration that is sufficient to reach a desired conversion of the remaining xylose.
  • part of the water and furfural is evaporated and furfural is enriched in the vapor stream.
  • the furfural vapors, produced in the second film evaporator 2 leave the film evaporator via pipe (23).
  • the vapors containing furfural can be condensed with (50) cooling water or with another stream which can be heated or can be used for heating a distillation column or the heat can be integrated in another manner, for example, to heat the prehydrolysate with or optionally without combining the streams.
  • the condensed furfural can be further separated and purified in a conventional furfural distillation and purification.
  • the concentrated hydrolysate 2 containing water, furfural and remaining xylose together with some intermediates, side products, heavies and sulfuric acid leaves the film evaporator via pipe (22) and is called concentrate 2.
  • This concentrate can be recycled to the first film evaporator 1 . In that case, a purge is needed to avoid blowing up the reaction section with heavies, optionally salts.
  • the concentrate 2 can also be recycled to the pretreatment. It can be neutralized and the furfural can be recovered and it can also be sent to the waste water treatment. In the latter 3 cases, at least part of the furfural will be recovered in addition, but in most cases it will require extra energy.
  • Example 3 3 film evaporators in series with heat integration via effect
  • a synthetic aqueous prehydrolysate (11) containing xylose is optionally preheated and is mixed with acid catalyst (optionally sulfuric acid) up to the appropriate acid concentration and brought into the film evaporator 1 .
  • acid catalyst optionally sulfuric acid
  • the film evaporator 1 is heated via indirect heat exchange with steam (15) up to a temperature above 170°C.
  • the condensate of the steam leaves the film evaporator via pipe 16.
  • part of the water and furfural is evaporated (for example, between 15% and 35% of the total liquid stream entering the first evaporator 1) and the vapors are enriched in furfural compared to the liquid phase. These vapors leave the film evaporator via pipe (13).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the film evaporator via pipe (12) and is called concentrate 1 .
  • Concentrate 1 is at a high temperature and can be optionally flashed in a flash vessel to the temperature of the second film evaporator 2 which is between 4 and 40°C below the temperature of the first film evaporator 1 and, after that, enters the second film evaporator 2.
  • the second film evaporator 2 operates at a temperature between 4 and 40°C below the temperature of first film evaporator 1 and is indirectly heated with the furfural containing vapors (13) of first film evaporator 1 .
  • the condensate of those furfural containing vapors leaves the second film evaporator 2 via pipe (17).
  • the residence time including optional recycle, is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose.
  • the second film evaporator 2 again part of the water and furfural is evaporated and furfural is enriched in the vapor stream. The furfural vapors leave the film evaporator via pipe 23.
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the second film evaporator 2 via pipe (22) and is called concentrate 2.
  • Concentrate 2 can be optionally flashed in a flash vessel to the temperature of a third film evaporator 3, which is between 4 and 40°C below the temperature of the second film evaporator 2 and, after that, enters the third film evaporator 3 via pipe (22).
  • the third film evaporator 3 operates at a temperature between 4 and 40°C below the temperature of the second film evaporator 2 and is indirectly heated with the furfural containing vapors (23) of second film evaporator 2.
  • the condensate of those furfural containing vapors leaves the third film evaporator 3 via pipe (27).
  • the residence time, including optional recycle, is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose.
  • the third film evaporator 3 again part of the water and furfural is evaporated and furfural is enriched in the vapor stream.
  • the furfural vapors leave the film evaporator via pipe (33).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the third film evaporator 3 via pipe (32) and is called concentrate 3.
  • the vapors containing furfural can be condensed with (50) cooling water or with another stream which can be heated or can be used for heating a distillation column or the heat can be integrated in another manner, for example, to heat the prehydrolysate with, or optionally without, combining the streams.
  • the condensed furfural can be further separated and purified in a conventional furfural distillation and purification.
  • the concentrated hydrolysate 3 containing water, furfural and remaining xylose together with some intermediates, side products, heavies and sulfuric acid leaves the film evaporator via pipe (32) and is called concentrate 3.
  • This concentrate 3 can be recycled to the first film evaporator 1 . In that case, a purge is needed to avoid blowing up the reaction section with heavies, optionally salts.
  • the concentrate can also be recycled to the pretreatment. It can be neutralized and the furfural can be recovered and it can also be sent to the waste water treatment. In the latter 3 cases, at least part of the furfural will be recovered in addition, but in most cases it will require extra energy.
  • Example 4 4 film evaporators in series with heat integration via effect
  • a synthetic aqueous prehydrolysate (11) containing xylose is optionally preheated and is mixed with acid catalyst (optionally sulfuric acid) up to the appropriate acid concentration and brought into the film evaporator 1 .
  • acid catalyst optionally sulfuric acid
  • the film evaporator 1 is heated via indirect heat exchange with steam (15) up to a temperature above 170°C.
  • the condensate of the steam leaves the film evaporator via pipe 16.
  • the total residence time including optional partial recycle over the film evaporator 1 was sufficient to reach a desired conversion of the xylose.
  • part of the water and furfural is evaporated (for example, between 10% and 25% of the total liquid stream entering the first evaporator 1) and the vapors are enriched in furfural compared to the liquid phase. These vapors leave the film evaporator via pipe (13).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the first film evaporator 1 via pipe (12) and is called concentrate 1 .
  • Concentrate 1 is at a high temperature and can be optionally flashed in a flash vessel to the temperature of the second film evaporator which is between 4 and 40°C below the temperature of the first film evaporator 1 and, after that, enters the second film evaporator 2.
  • the second film evaporator 2 operates at a temperature between 4 and 40°C below the temperature of the first film evaporator 1 and is indirectly heated with the furfural containing vapors (13) of the first film evaporator 1 .
  • the condensate of those furfural containing vapors leaves the second film evaporator 2 via pipe (17).
  • the residence time is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose
  • the residence time is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose
  • the second film evaporator 2 again part of the water and furfural is evaporated and furfural is enriched in the vapor stream.
  • the furfural vapors leave the film evaporator via pipe 23.
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the second film evaporator 2 via pipe (22) and is called concentrate 2.
  • Concentrate 2 can be optionally flashed in a flash vessel to the temperature of the third film evaporator 3 which is between 4 and 40°C below the temperature of the second film evaporator 2 and, after that, enters the third film evaporator 3 via pipe (22).
  • the third film evaporator 3 operates at a temperature between 4 and 40°C below the temperature of the second film evaporator 2 and is indirectly heated with the furfural containing vapors (23) of the second film evaporator 2.
  • the condensate of those furfural containing vapors leaves the third film evaporator 3 via pipe (27).
  • the residence time, including optional recycle, is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose.
  • the third film evaporator 3 again part of the water and furfural is evaporated and furfural is enriched in the vapor stream.
  • the furfural vapors leave the third film evaporator 3 via pipe (33).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the third film evaporator 3 via pipe (32) and is called concentrate 3.
  • Concentrate 3 can be optionally flashed in a flash vessel to the temperature of the fourth film evaporator 4 which is between 4 and 40°C below the temperature of the third film evaporator 3 and, after that, enters the fourth film evaporator 4 via pipe (32).
  • the fourth film evaporator 4 operates at a temperature between 4 and 40°C below the temperature of the third film evaporator 3 and is indirectly heated with the furfural containing vapors (33) of the third film evaporator 3.
  • the condensate of those furfural containing vapors leaves the fourth film evaporator 4 via pipe (37).
  • the residence time including optional recycle, is at a temperature, and higher acid concentration that are sufficient to reach a desired conversion of the remaining xylose.
  • the fourth film evaporator 4 again part of the water and furfural is evaporated and furfural is enriched in the vapor stream. The furfural vapors leave the film evaporator via pipe (43).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the fourth film evaporator 4 via pipe (42) and is called concentrate 4.
  • the vapors containing furfural can be condensed with (50) cooling water or with another stream which can be heated or can be used for heating a distillation column or the heat can be integrated in another manner, for example, to heat the prehydrolysate with or optionally without combining the streams.
  • the condensed furfural can be further separated and purified in a conventional furfural distillation and purification.
  • the concentrated hydrolysate 4 containing water, furfural and remaining xylose together with some intermediates, side products, heavies and sulfuric acid leaves the fourth film evaporator 4 via pipe (42) and is called concentrate 4.
  • This concentrate 4 can be recycled to the first film evaporator 1 . In that case, a purge is needed to avoid blowing up the reaction section with heavies, optionally salts.
  • the concentrate 4 can also be recycled to the pretreatment. It can be neutralized and the furfural can be recovered and it can also be sent to the waste water treatment. In the latter 3 cases, at least part of the furfural will be recovered in addition, but in most cases it will require extra energy.
  • Example 5 one film evaporator
  • a synthetic aqueous prehydrolysate containing xylose is optionally preheated and is mixed with acid catalyst (optionally sulfuric acid) up to the appropriate acid concentration and brought into the film evaporator 1 via 11 .
  • acid catalyst optionally sulfuric acid
  • the film evaporator 1 is heated via indirect heat exchange with steam (15) up to a temperature above 170°C.
  • the condensate of the steam leaves the film evaporator 1 via pipe 16.
  • the total residence time including optionally partial recycle over the film evaporator 1 (not shown) was sufficient to reach a desired conversion of the xylose.
  • part of the water and furfural is evaporated (for example, between 20% and 50% of the total liquid stream entering the film evaporator 1) and the vapors are enriched in furfural compared to the liquid phase. These vapors leave the film evaporator via pipe (13).
  • the concentrated hydrolysate containing water, furfural and xylose together with some intermediates, side products, heavies and sulfuric acid leaves the film evaporator 1 via pipe (12) and is called concentrate 1 .
  • Concentrate 1 may recycle to the film evaporator 1 in order to increase the total residence time in film evaporator 1 .
  • the overall length of the film evaporator 1 may be increased, again to increase the total residence time in film evaporator 1 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

La présente invention concerne un procédé de production de furfural à partir d'un matériau de départ contenant du pentose ou du pentosane dans un évaporateur à film.
PCT/EP2024/066427 2023-06-13 2024-06-13 Procédé de production de furfural Pending WO2024256571A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23178934.8 2023-06-13
EP23178934 2023-06-13

Publications (1)

Publication Number Publication Date
WO2024256571A1 true WO2024256571A1 (fr) 2024-12-19

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369655A (en) 1940-08-13 1945-02-20 Masonite Corp Process of making furfural and fatty acids
EP0124507B1 (fr) 1983-05-02 1989-06-28 Lenzing Aktiengesellschaft Procédé pour l'obtention du furfural à partir des eaux résiduaires acides de la préparation de la cellulose et appareillage pour la mise en oeuvre de ce procédé
WO2006095340A1 (fr) 2005-03-07 2006-09-14 I.D.E. Technologies Ltd. Evaporateur a effets multiples
US20120108829A1 (en) 2010-10-27 2012-05-03 Technische Universiteit Delft Process for the production of furfural from pentoses
WO2015175840A1 (fr) 2014-05-16 2015-11-19 Chapman/Leonard Studio Equipment, Inc. Voie de dolly de caméra pliante et de largeur réglable
US20200369636A1 (en) * 2017-12-06 2020-11-26 Eco Environmental Energy Research Institute Limited System and Method for Continuously Preparing Furfural Using Acid-Containing Pentose Solution

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369655A (en) 1940-08-13 1945-02-20 Masonite Corp Process of making furfural and fatty acids
EP0124507B1 (fr) 1983-05-02 1989-06-28 Lenzing Aktiengesellschaft Procédé pour l'obtention du furfural à partir des eaux résiduaires acides de la préparation de la cellulose et appareillage pour la mise en oeuvre de ce procédé
WO2006095340A1 (fr) 2005-03-07 2006-09-14 I.D.E. Technologies Ltd. Evaporateur a effets multiples
US20120108829A1 (en) 2010-10-27 2012-05-03 Technische Universiteit Delft Process for the production of furfural from pentoses
WO2012057625A2 (fr) 2010-10-27 2012-05-03 Technische Universiteit Delft Procédé de production de furfural à partir de pentoses et/ou de pentosanes hydrosolubles
WO2015175840A1 (fr) 2014-05-16 2015-11-19 Chapman/Leonard Studio Equipment, Inc. Voie de dolly de caméra pliante et de largeur réglable
US20200369636A1 (en) * 2017-12-06 2020-11-26 Eco Environmental Energy Research Institute Limited System and Method for Continuously Preparing Furfural Using Acid-Containing Pentose Solution

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