(19)
(11)EP 3 386 958 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
09.09.2020 Bulletin 2020/37

(21)Application number: 16810305.9

(22)Date of filing:  07.12.2016
(51)International Patent Classification (IPC): 
C07D 307/68(2006.01)
(86)International application number:
PCT/EP2016/080107
(87)International publication number:
WO 2017/097843 (15.06.2017 Gazette  2017/24)

(54)

PROCESS FOR THE PRODUCTION OF 2,5-FURANDICARBOXYLIC ACID (FDCA)

VERFAHREN ZUR HERSTELLUNG VON 2,5-FURANDICARBOXYLSÄURE (FDCA)

PROCÉDÉ POUR LA PRODUCTION DE L'ACIDE 2,5-FURANEDICARBOXYLIQUE (FDCA)


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 10.12.2015 EP 15199377

(43)Date of publication of application:
17.10.2018 Bulletin 2018/42

(73)Proprietors:
  • Annikki GmbH
    8074 Raaba-Grambach (AT)
  • Novolana GmbH
    8144 Tobelbad (AT)

(72)Inventors:
  • TEKAUTZ, Günter
    8020 Graz (AT)
  • KIRSCHNECK, Dirk
    8200 Albersdorf-Prebuch (AT)
  • LINHART, Walter
    8010 Graz (AT)

(74)Representative: Nemec, Harald 
Schwarz & Partner Patentanwälte Wipplingerstrasse 30
1010 Wien
1010 Wien (AT)


(56)References cited: : 
WO-A1-2012/161967
JP-A- 2009 013 079
WO-A1-2014/122319
  
  • MARCELO L. RIBEIRO ET AL: "Cooperative effect of cobalt acetylacetonate and silica in the catalytic cyclization and oxidation of fructose to 2,5-furandicarboxylic acid", CATALYSIS COMMUNICATIONS, vol. 4, no. 2, 1 February 2003 (2003-02-01), pages 83-86, XP055008814, ISSN: 1566-7367, DOI: 10.1016/S1566-7367(02)00261-3
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Field of the invention



[0001] The present invention relates to a process of oxidizing 5-Hydroxymethylfurfural available in a solvent or solvent mixture containing at least one aprotic high boiling, polar solvent (hbS) producing 2,5-furandicarboxylic acid.

State of the art



[0002] 2,5-furandicarboxylic acid (hereinafter referred to as FDCA) is accessible from renewable resources and it is an interesting intermediate for molecules in various applications like agricultural chemicals, drugs, pesticides, pharmacology or antibacterial agents. The most important group of FDCA conversions is the polymerisation to polyamides, polyesters or polyhydrazines. (Lewkowski, 2001)

[0003] Catalytic oxidation of 5-hydroxymethylfurfural (hereinafter referred to as HMF) derived from dehydration of hexoses is potentially the most important way to synthesize FDCA from renewable resources. A lot of different approaches for the oxidation of HMF yielding FDCA as main product are known in the literature. But there is no process described making an easy coupling of HMF formation and oxidation possible. This is mainly due to different types of solvents used for these steps.

[0004] The HMF oxidation to FDCA, in the first step, runs over diformylfuran (hereinafter referred to as DFF) or hydroxymethylfurancarboxylicacid (HMFCA) and in the following step over formylfurancarboxylic acid (FFCA). The principal scheme is shown below:



[0005] Most commonly the oxidation is carried out in water, alcohols or carboxylic acids. US 3,326,944 describes the oxidation of HMF to FDCA in water with sodium hydroxide and platinum type catalysts (hereinafter referred to as PTC).

[0006] EP 0 356 703 describes the oxidation of HMF in an aqueous environment with PTC and at pH value of maximum 8. This value is controlled during the process by continuous addition of base.

[0007] In US 8,193,382 the same oxidation in water or acetic acid is documented. Weak bases like carbonates or phosphates are used as bases in this case. Catalysts used for this process are also PTC.

[0008] US 8,865,921 describes a Co/Mn/Br catalytic system, which is also used for terephthalic acid synthesis, for oxidation of HMF, but also of HMF esters, 5-(chloromethyl)furfural and other related compounds. These processes are also carried out in acetic acid or mixtures of acetic acid with water. The same chemical system and solvents with different technical approaches are described in patent US 8,242,292, which describes an improvement by continuous removal of water, and WO 2013/033058, in which the reaction is carried out in a spray reactor. Both processes run in acetic acid or acetic acid/water mixtures.

[0009] Oxidation of HMF in aprotic media has been described only for the purpose of selective oxidation to diformylfuran. US 7,700,788 describes the oxidation of HMF to DFF in methylene chloride.

[0010] The starting material for the oxidation step at issue here, HMF, is an important intermediate achieved from dehydration of hexoses (glucose, fructose). This synthesis in opposite to the oxidation is usually not carried out in water due to low yields. Maximum HMF yields achieved in water lie in the range between 50% and 60%.

[0011] Tuercke et al. (2009) describe a continuous, HCl catalyzed microreactor process in water yielding 54% HMF.

[0012] High selectivities for the dehydration of fructose or glucose are achieved only in high boiling, polar, aprotic solvents such as Dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidon (NMP), N,N-Dimethylformamide (DMF) or N,N-Dimethylacetamide (DMA).

[0013] Nowadays, mainly DMSO is used as a solvent, as described in US 4,590,283 (Roquette Freres). But also DMF, DMA or NMP show high selectivities and excellent yields, as described in the same document or in more recent ones like EP 2 703 395 or US 7,317,116 B2.

[0014] For these processes, in order to go into the oxidation step, removal of the high boiling solvent or at least a significant amount thereof is necessary.

[0015] Another approach employs water as solvent and biphasic systems to extract HMF to the organic phase in order to avoid rehydration. Such approaches show excellent results up to 90% HMF yield. Still, however, in order to achieve such good results, an addition of DMSO or NMP to the water phase is necessary. This solvent is then also extracted to the organic phase and needs to be separated from the HMF, making the process economically unfavored. The improvements of this approach only lies in the smaller amount of high boiling solvent that needs to be removed. See (Chheda et al., 2007).

[0016] A review of the scientific literature to HMF formation from hexoses separated to aqueous media and polar aprotic solvents is given by (Teong et al., 2014).

[0017] PCT-application PCT/EP2015/063578 (not pre-published) discloses the selective production of oxidized furan derivatives starting from HMF wherein the oxidation process is carried out continuously in flow, there are provided means for varying reaction parameters, the solvent for the oxidation process is water and a dipolar aprotic solvent. Especially NMP is present as a co-solvent.

[0018] At the actual state of the art the step of HMF oxidation has to be done in a different solvent as the previous HMF formation if both steps should reach high yields. Usually HMF is isolated after dehydration before being forwarded to the oxidation step, which needs high effort to separate the high boiling solvent and leads to a decrease of the HMF yield.

[0019] Solvent removal can be accomplished by evaporation. However, it was found that in doing so it is necessary to keep temperatures below 50°C to avoid decomposition of HMF. Accordingly very low pressures are necessary to be able to remove the high boiling solvents. This is nearly impossible and very expensive to be done for large scale industrial processes.

[0020] An alternative approach is the extraction of the high boiling solvent. However, the solubility of HMF in organic solvents capable to extract polar, high boiling solvents is good and, thus, large amounts of HMF are lost to the organic phase.

[0021] To avoid obvious problems with separation of HMF from high boiling polar solvents, several different approaches were taken.

[0022] Bicker (Bicker et al., 2005) described dehydration in supercritical fluids like different acetone/water mixtures, achieving full conversion and yields of 77%.

[0023] EP 1 427 715 B2 describes a one pot synthesis of DFF from a carbohydrate. In the first step the dehydration to HMF is done and in the second the oxidation to DFF with vanadium compounds as catalyst.

[0024] Also the oxidation of HMF to DFF in DMSO can be found in the literature, as described by Grasset et al. (2013), using intercalated vanadium phosphate oxides as catalyst, or by Amarasekara et al. (2008), using Mn(III)-salen catalysts. An oxidation of HMF to FDCA in these systems is not described.

[0025] It would be advantageous to go directly from the dehydration step to the oxidation step without additional work-up in order to achieve an economical process.

[0026] Ribeiro et al (2003) have proposed a one pot reaction in labscale from fructose to FDCA with cobalt acetylacetonate in a sol-gel silica as catalyst. They achieved excellent yield of 72% over both steps. Still, the viability of this reaction system for large scales is questionable.

[0027] To the present inventor's best knowledge, up to now no technical feasible method was described to combine the synthesis of HMF with a subsequent oxidation of HMF without costly work-up in between.

[0028] This problem is solved by the process according to claim 1. Advantageous embodiments of the present invention are disclosed in the sub-claims.

Brief description of the drawings:



[0029] 

Figure 1 is a process diagram exemplifying a preferred embodiment of the present invention.

Figure 2 shows the result of extraction trials regarding the extraction of NMP

Figure 3 shows the result of extraction trials regarding the extraction of DMSO.


Detailed Description of the invention



[0030] Surprisingly, the present inventors have found an improved economical process that enables to oxidize HMF in aprotic high boiling, polar solvents to FDCA without the need to isolate or concentrate HMF before the oxidation step.

[0031] Accordingly, in one aspect the present invention relates to a process for the production of 2,5-furandicarboxylic acid (FDCA) via oxidation of 5-hydroxymethyl-2-furfural (HMF), said HMF being present in a solution in an aprotic high-boiling polar solvent and water, wherein said process is characterized by the combination of
  • a first oxidation step wherein the HMF is at least partly oxidized in said solution to yield a first reaction mixture comprising at least one monoacid selected from the group consisting of 5-hydroxymethylfuran-2-carboxylic acid (HMFA) and 5-formylfuran-2-carboxylic acid (FFCA) and, optionally, FDCA
  • an extraction step after the first oxidation step wherein said aprotic high-boiling polar solvent is extracted from said first reaction mixture by means of an extraction solvent, wherein said at least one monoacid remains in an aqueous phase,
  • a second oxidation step wherein said at least one monoacid is oxidized to FDCA.


[0032] For the purposes of the present invention, a "high-boiling polar solvent" (in the following also abbreviated as "hbs") means a solvent that has a boiling point higher than water and is miscible with water.

[0033] The high-boiling polar solvent is a polar aprotic solvent. The skilled artisan understands that solvents having a permittivity of 5 or more, in particular 15 or more, are considered to be polar and that solvents containing no hydrogen atoms that can be donated into a hydrogen bond are considered to be aprotic. Preferred are polar aprotic solvents all hydrogen atoms of which (if any) are covalently bound to a carbon atom.

[0034] More preferably, the high-boiling aprotic polar solvent is selected from the group consisting of Dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), N,N-Dimethylformamide (DMF) or N,N-Dimethylacetamide (DMA) and mixtures thereof. The most preferred solvent is NMP

[0035] It has surprisingly been found that it is possible to carry out oxidation of HMF to FDCA without the need of prior removal of the aprotic high boiling polar solvent of a preceding step to obtain HMF by a three-step process:
In the first step, HMF is oxidized in a mixture of aprotic high boiling polar solvent and water as completely as possible to at least one of the monoacid oxidation products of HMF (FFCA, HMFCA) and, eventually also already in part FDCA. Especially, in the first step a mixture of FFCA, HMFCA and FDCA may be obtained.

[0036] The second step is the extraction of the aprotic high boiling polar solvent from an alkaline solution leaving the salts of the monoacids and the FDCA completely in the aqueous phase. Any unreacted HMF from the first step as well as DFF as by-product of the first step are transferred into the organic phase of this extraction.

[0037] In the third step, the oxidation of the monoacids to FDCA is completed in water. All three steps can be done in a batchwise operation as well as in a continuous one.

[0038] For the first oxidation step, a partial oxidation of HMF is performed at mild conditions. High pressures, high temperatures, high basicity or high base concentrations can be avoided as no complete conversion to FDCA is targeted. The conditions in this step are selected to avoid DFF formation and maximize formation of monoacids and FDCA.

[0039] Especially, it has been found that while it would be principally possible to oxidize the HMF to FDCA in one step by employing strong bases, certain amounts of HMF are degraded during the reaction, resulting in solid impurities that may block the reactor, thus making this option unsuitable especially in the case of a continuous reaction design.

[0040] Thus, it has been found to be advantageous to employ weak bases, such as with a pKa value of from 7.5 to 13 in the first oxidation step. The base is preferably selected from the group consisting of carbonates and phosphates, especially anorganic carbonates and phosphates. Most preferably, Na3PO4 and/or Na2HPO4 is employed as a base.

[0041] The pH value for the first oxidation step may in particular be between 10 and 12. The molar amount of the base employed may be at least twice the molar amount of HMF to ensure deprotonation of the acid group.

[0042] Thus, the conditions are selected such that the acidic groups formed in the oxidation step are transferred into salt form as completely as possible, only the salt from being soluble in the aqueous solution.

[0043] Furthermore, the usage of certain amounts of water has been found to be advantageous.

[0044] If no water is already present in the reaction mixture of a preceding HMF production, it has to be added for this oxidation step. This simply can be done together with the base addition. The water content in the solution may range between 1 and 80%. More preferable is a water content of 40 to 60%.

[0045] Further preferred conditions for the first oxidation step are:
  • the oxidant is air or oxygen
  • the molar excess of oxygen to HMF is 0.5 to 1.5 times, preferably 0.9 to 1.4 times, most preferred 1.25 times
  • the reaction pressure is in a range of 1 bar to 100 bar, preferably 5 bar to 40 bar, most preferred 20 bar
  • the temperature is in a range of from 50°C to 130°C, preferably 60°C to 100°C, most preferred 90°C
  • the residence time during the reaction is 30 minutes or less, preferably 15 minutes or less


[0046] Only part of the above parameters may be set as detailed above. Preferably, a combination of several or, most preferably, all of the above conditions may be applied.

[0047] The catalyst to be used for the first oxidation step may be any suitable oxidation catalyst, such as platinum type catalysts (PTC), CuO/AgO, CuO or CoO. Preferably a mixed copper oxide/silver oxide catalyst is used.

[0048] The reaction medium (RM1) obtained in the first oxidation step contains mainly HMFCA, FFCA and FDCA.

[0049] In the second step the aprotic high boiling polar solvent is extracted with a suitable low boiling organic solvent (Extraction). Unreacted HMF and DFF go into the organic phase, whereas the salts of the monoacids (HMFCA, FFCA) and the target product FDCA remain in the water phase.

[0050] The extraction solvent for the extraction step is preferably a low boiling solvent, and more preferably is selected from ethylacetate, trichloromethane and mixtures thereof. These solvents showed excellent results with regard to necessary solvent amount and number of extraction steps in the extraction of the aprotic high boiling polar solvent from the reaction mixture. A batchwise as well as a continuous extraction is viable.

[0051] The aqueous phase obtained in the extraction step is subjected to a second oxidation step in order to complete the oxidation to FDCA. The second oxidation step can be carried out employing more harsh conditions as compared with the first oxidation step in order to complete the oxidation of the monoacids. HMF and DFF, being the most unstable compounds in the process, are no longer available in the reaction mixture at this stage. Additionally, the presence of water as a solvent at this stage avoids problems of possible spontaneous solvent oxidation at high concentrations of the oxidizing agent and safety issues connected therewith. Furthermore, possible deprotonation initiated decomposition reactions of the aprotic high boiling polar solvent with strong bases, leading to precipitates and a loss of expensive solvent, can be avoided this way.

[0052] Thus, for the second oxidation step, any base can be used to keep the pH value in a basic regime of between 7.0 to 14.0, and more preferable between 10.0 and 12.0. More preferably, sodium or potassium hydroxide are used.

[0053] Further preferred conditions for the second oxidation step are:
  • the oxidant is air or oxygen
  • the molar excess of oxygen to HMF is 0.5 to 5 times preferably 1.0 to 3.0 times, most preferred 2.0 times
  • the reaction pressure is in a range of 1 bar to 100 bar, preferably 5 bar to 40 bar, most preferred 20 bar
  • the temperature is in a range of from 80°C to 180°C, preferably 90°C to 130°C, most preferred 110°C
  • a base with a pKa value of above 13, most preferably NaOH, is employed
  • the residence time during the reaction is 30 minutes or less, preferably 15 minutes or less


[0054] Again, only part of the above parameters may be set as detailed above. Preferably, a combination of several or, most preferably, all of the above conditions is applied.

[0055] The catalyst for the second oxidation step, again, may be any suitable oxidation catalyst. Preferably, platinum based catalysts are employed.

[0056] The FDCA obtained in the second oxidation step may be converted to the free acid by means of an aqueous acid. The free acid precipitating from the reaction mixture may be isolated by means of filtration.

[0057] As mentioned above, according to a preferred embodiment of the present invention, in said first oxidation step parts of the HMF remain unreacted and/or are oxidized to 2,5-diformylfuran (DFF) and in said extraction step said unreacted HMF and/or said DFF are extracted from said first reaction mixture.

[0058] Said extracted unreacted HMF and/or said extracted DFF are preferably recycled to the solution before the first oxidation step.

[0059] A further preferred embodiment of the present invention is characterized in that, after the extraction step, the extraction solvent and the aprotic high boiling polar solvent are separated from each other.

[0060] Especially, both extraction solvent and aprotic high boiling polar solvent may be recycled. The recycling ratio may be in a range of from 40 to 99%.

[0061] The separation may be carried out by distilling off the low boiling extraction solvent. The extraction solvent can be recycled into the extraction step.

[0062] The aprotic high boiling polar solvent may be recycled to a preceding HMF synthesis step. Especially in case the aprotic high boiling polar solvent contains significant amounts of unreacted HMF and/or DFF after the extraction step, the aprotic high boiling polar solvent may also be recycled to the first oxidation step. Before being recycled, the aprotic high boiling polar solvent may be purified. Any water immiscible organic solvent can be used to extract the aprotic high boiling polar solvents at this stage.

[0063] The process of the present invention may be carried out batchwise or in a continuous fashion. The process of the present invention is especially advantageous in the context of a continuous process design. In this regard, the process of the present invention can advantageously be combined with a preceding process for obtaining HMF, especially if also this preceding step is carried out in a continuous fashion.

[0064] Figure 1 shows a process diagram exemplifying a preferred embodiment of the present invention:
A mixture of fructose and aprotic high-boiling polar solvent (1) and a mixture of HCl and water (2) are fed to a dehydration step (A). In the dehydration step (A), HMF in a mixture of water and aprotic high-boiling polar solvent is obtained.

[0065] This mixture is subjected to a first oxidation step (B), employing an aqueous base, and air or oxygen as oxidation agent (3).

[0066] The mixture obtained from the first oxidation (B), containing HMFCA and/or FFCA and, optionally FDCA, as well as residual HMF and DFF, is subjected to an extraction step (C) employing an extraction solvent 4.

[0067] The organic phase obtained after extraction, containing the HMF, DFF, the aprotic high-boiling polar solvent as well as the extraction solvent may be subjected to a distillation step (g). Aprotic high boiling polar solvent, optionally containing HMF and DFF, is recycled to the starting solution (1) in large part.

[0068] The extraction solvent is recycled to the extraction step (4).

[0069] The water phase containing HMFCA and/or FFCA and, optionally, FDCA is subjected to the second oxidation (D) step utilizing an aqueous solution of a strong base and air or oxygen as oxidizing agent (5).

[0070] Upon completion of the oxidation, the reaction mixture is neutralized or acidified (E) with an aqueous acid (6) to convert the FDCA salt into free acid, which precipitates from the aqueous phase.

[0071] In a filtration step (F) solid FDCA is obtained from the reaction mixture.

Examples


1.) NMP/NaOH/Pt-C/air/22bar/90°C


i) Oxidation 1 - in NMP, Pt-C, 17 bar and 80°C, NaOH



[0072] The starting solution A is prepared by dissolving 5-Hydroxymethylfurfural (99%) in 95g NMP (99,5%, Sigma Aldrich) and 5g deionized water. The starting solution B is a 15% NaOH solution, prepared from 150.41g NaOH and 850.18g deionized water.

[0073] In a continuous flow plant, solution A and solution B are contacted in a 1/16" t-piece. The flow rate for solution A is 0.08 ml/min, and for solution B 0.06 ml/min. The mixture obtained is directly contacted with 125 ml/min air flow, before the mixture enters the actual reactor. In this case the reactor was a trickle bed reactor using platinum on activated carbon as catalyst. The double jacketed reactor is heated to 80°C and provides a residence time of 30 minutes for the given flow rates. The whole system is pressurized to 22 bar with a pressure maintaining valve.

[0074] The reaction mixture obtained in this step contains no HMF. The oxidation product mixture contains, according to HPLC analysis, FDCA: 73.67%, HMFCA: 18.10%, FFCA: 7.67%, DFF: 0.41% and 0.15% unknown oxidation products. Additionally, a small amount of dark, solid material is yielded using this procedure, leading to a reduced lifetime cycle of the catalyst fixed bed.

ii.) Extraction with ethyl acetate



[0075] The reaction mixture (20.4ml) collected from the first oxidation step was extracted six times using 20 ml ethyl acetate per cycle to remove NMP. The HPLC chromatogram showed no loss of the acids in the aqueous phase after this procedure. The DFF was transferred completely to the organic phase.

iii.) Oxidation 2 - in H2O, Pt-C, 17 bar and 80°C, NaOH



[0076] The aqueous solution of the acids (FCDA, HMFCA and FFCA) obtained from the extraction is pumped with a flow rate of 0.08 ml/min into a t-piece mixer to be mixed with a stream of 0.06 ml/min 15% caustic solution in a t-piece mixer. This basic mixture is contacted with air in a t-piece. (flow rate air is 125 mln/min). This mixture is led into the trickle bed reactor filled with platinum on activated charcoal as catalyst. The hold up time in the reactor is 30 minutes at 100°C. The whole plant setup is kept at a pressure of 25 bar.

[0077] Sampling was done continuously at room temperature. The reaction mixture obtained contained 100.0% FDCA according to the HPLC spectra. The yield of the overall process according to quantitative HPLC analytics was 82%.

2.) DMSO/Na2HPO4/Pt-C/air/17 bar/80°C


i) Oxidation 1 - in DMSO, Pt-C, 17 bar and 80°C, Na2HPO4



[0078] The process was carried out in an equivalent continuous lab-plant setup as in example 1. Starting solution A was prepared by mixing 32.8g HMF and 200.3g DMSO; solution B was a 11.5% solution of disodium hydrogenphosphate prepared by making a saturated mixture (38.15g Na2HPO4 and 45g of deionized water) diluted with deionized water twice in volumetric ratio of 1:1.

[0079] The processing parameters were 30 minutes residence time at 80°C and 18 bar. The catalyst used was platinum on activated carbon.

[0080] The oxidation product mixture contains, according to HPLC analysis, FDCA: 9.33%, HMFCA: 4.11%, FFCA: 27.67%, DFF: 16.23% and 41.70% of HMF. About 1% are unidentified side products.

ii.) Extraction with trichloromethane



[0081] DMSO extraction was carried out with trichloromethane. 21.1ml reaction mixture was extracted six times with 20ml trichloromethane in each cycle.

[0082] DFF was extracted completely to the organic phase. The acids remained completely in the water phase, as well as some unreacted HMF (4.7% according to HPLC).

iii.) Oxidation 2 - in H2O, Pt-C, 17 bar and 80°C, NaOH



[0083] The water phase from the extraction step was processed in a second oxidation step. The flow rates in this step were 0.08 for the reaction mixture from the extraction, 0.06 for the aqueous 11,5% Na2HPO4 solution and 125mln/min air. The catalyst used was platinum on activated carbon, and the processing parameters were 100°C and 22 bar.

[0084] The achieve reaction mixtures contained 57.80% FDCA, 13.64% HMFCA and 23.14% FFCA. The yield for the overall process was determined by quantitative HPLC to be 37%.

3.) NMP/Na2HPO4/CuO/Al2O3/air/17 bar/80°C


i) Oxidation 1 - in NMP, Pt-C, 17 bar and 80°C, Na2HPO4



[0085] The process was carried out in a comparable, scaled up continuous lab-plant setup as used in the examples above. Starting solution A was prepared by mixing 65.6g HMF and 400.0g NMP; solution B was a 15% solution of sodium phosphate, prepared by mixing 150.0g Na2HPO4 and 850.0g of deionized water.

[0086] The flow rates used in this trial were 2.86ml/min solution A, 2.14ml/min solution B and 250.0nml/min for air. Further processing parameters were 10 minutes residence time at 90°C and 18 bar. The catalyst used was copper oxide on aluminium oxide.

[0087] The oxidation product mixture obtained from this trial contains, according to HPLC analysis, FDCA: 9.20%, HMFCA: 86.39%, FFCA: 0.13%, DFF: 0.36% and 2.82% of HMF. About 1% are unidentified side products.

ii.) Extraction with ethyl acetate



[0088] NMP extraction was carried out with ethyl acetate. 50ml reaction mixture was extracted six times with 40ml ethyl acetate in each cycle.

[0089] FDCA, HMFCA and FFCA remained completely in the water phase. Also a small amount of HMF was found in the water phase (0.5% according to HPLC). DFF completely went into the organic phase and was discarded.

iii.) Oxidation 2 - in H2O, Pt-C, 17 bar and 90°C, NaOH



[0090] The water phase from the extraction step was processed in a second oxidation step in the smaller lab scale setup used also in example 1 and 2. Flow rates in this step were again 0.08ml/min for the reaction mixture from the extraction, 0.06ml/min for the aqueous 15% NaOH solution and 125mln/min air. The catalyst used was platinum on activated carbon, and the processing parameters were 100°C and 22 bar.

[0091] According to HPLC analysis, the achieved reaction mixtures contained 99.51% FDCA, 0.34% HMFCA and about 0.1% unknown side products. The yield for the overall process was determined by quantitative HPLC to be 85%.

4.) NMP/NaOH/CuO-AgO/air/22bar/90°C


i) Oxidation 1 - in NMP, CuO-AgO, 17 bar and 90°C, NaOH



[0092] The same continuous lab-plant setup as for example 1 and 2 was used for this experiment. Solution A was prepared from 16.4g of HMF and 100g of NMP. Solution B was a 15% solution of sodium hydroxide in water.

[0093] Flow rates for solution A was 0.08ml/min, and 0.06ml/min for solution B; for the air flow it was 125ml/min. Mixing was done in a t-piece mixers, and reaction took place in a trickle bed reactor. 90°C and 22 bar were adopted to the reactor and the hold up time was 15 minutes.

[0094] The catalyst used in this experiment was CuO/AgO catalyst on alumina. This catalyst was prepared according to literature (Tian et al., 2008).

[0095] During the experiment a slow pressure rise in the system due to plugging with insoluble humic matter is observed, leading also to reduced conversion after six hours plant operation time.

[0096] The oxidation product mixture contains according to HPLC analysis FDCA: 27.65%, HMFCA: 71.37%. No HPLC detectable amounts of FFCA, DFF or HMF were found.

ii.) Extraction with ethyl acetate



[0097] 20.9ml of the reaction mixture were contacted six time with 20ml ethyl acetate each to extract NMP from the water phase.
HPLC analysis shows that FDCA and HMFCA remained completely in the water phase.

iii.) Oxidation 2 - in H2O, Pt-C, 17 bar and 80°C, NaOH



[0098] The second oxidation step was done in a similar setup as in the first oxidation step and with the same parameters. Changed was only the catalyst in the reactor back to platinum on activated carbon.

[0099] The achieve reaction mixture contained 93.65% FDCA, 5.26% HMFCA and about 1% unidentified side products or intermediates. The yield of the overall oxidation process was determined by HPLC to be 88%. However, this yield could not be established for longer process times because of the plugging observed in the first oxidation step due to black tar formation.

5.) Extraction trials


i) NMP extraction from water phase with different solvents



[0100] A mixture of 24.12g NMP (53%(w/w), hatched bar in figure 2) and 21.2g deionized water were prepared as starting solution for separating NMP from water.

[0101] This solution was transferred into a separating funnel. 21.2g of ethylacetate were added to the NMP solution, both phases were intensively contacted and then separated. The mass of the single phases were recorded and a small sample was taken from the water phase to determine NMP content by quantitative HPLC chromatography.

[0102] This procedure was repeated five times for the water phase with the same amount of fresh solvent in each step to achieve an overall of six discrete extraction steps. The remaining NMP content in the water phase was determined by quantitative HPLC chromatography.

[0103] The NMP extraction as described above for ethyl acetate was carried out with identical ratios also with dibutyl ether, toluene, tetrahyfrofuran, trichloromethane and n-butanol.

[0104] With ethyl acetate (data set 1 in figure 2), a remaining NMP concentration of 5.7% (dotted bar in figure 2) was reached. This corresponds to a removal of 89.8% of the NMP from the water phase in six extraction steps (horizontal line bar in figure 2). This result was beaten by trichloromethane (data set 4), which removed NMP from the water phase to an extent that it was not detectable anymore. Dibutyl ether (data set 2, 11.5%) and toluene (data set 3, 21.9%) showed significantly worse results. Tetrahydrofuran (data set 5) and n-butanol (data set 6) ended up with a one phase system.

[0105] The result is summarized in figure 2. The hatched bar in this figure corresponds to the NMP starting concentration, the dotted bar to the NMP concentration after six extraction steps and the horizontal line bar to the relative amount of NMP removed in the six steps.

ii) DMSO extraction from water phase with different solvents



[0106] 17.28g DMSO and 15.13g deionized water were mixed and transferred into a separation funnel. 15.20g ethyl acetate were added to this solution. The two-phase system was intensely mixed for ten minutes and then the phases separated.

[0107] The masses of both phases were recorded and a sample from the water phase was taken to be analysed in quantitative HPLC.

[0108] Extraction of NMP from the waterphase was repeated five times with 15.2g of ethyl acetate in each step. After each single step masses were recorded and quantitative HPLC measurements were done.

[0109] The same extraction procedure as described for ethyl acetate was carried out also with dibutyl ether, toluene, trichloromethane, tetrahydrofuran and n-butanol.

[0110] The results are summarized in figure 3. Assignment of bars is identical to figure 2 described above.

[0111] 16.4% of the DMSO was removed from the water phase with ethyl acetate (data set 1 in figure 3). Better results were achieved with trichloromethane (data set 4, 28.3%) and tetrahydrofuran (data set 5, 22.5%). Toluene (data set 3, 8.1%) and dibutylether (data set 2, 6.7%) showed an even lower DMSO removal capability. N-butanol (data set 6) did show no phase separation.


Claims

1. A process for the production of 2,5-furandicarboxylic acid (FDCA) via oxidation of 5-hydroxymethyl-2-furfural (HMF), said HMF being present in a solution in an aprotic, high-boiling polar solvent and water, characterized by the combination of

- a first oxidation step wherein the HMF is at least partly oxidized in said solution to yield a first reaction mixture comprising at least one monoacid selected from the group consisting of 5-hydroxymethylfuran-2-carboxylic acid (HMFA) and 5-formylfuran-2-carboxylic acid (FFCA) and, optionally, FDCA

- an extraction step after the first oxidation step wherein said aprotic high-boiling polar solvent is extracted from said first reaction mixture by means of an extraction solvent, wherein said at least one monoacid remains in an aqueous phase,

- a second oxidation step wherein said at least one monoacid is oxidized to FDCA.


 
2. A process according to claim 1 , characterized in that the high-boiling aprotic polar solvent is selected from the group consisting of Dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), N,N-Dimethylformamide (DMF) or N,N-Dimethylacetamide (DMA) and mixtures thereof.
 
3. A process according to any of the preceding claims, characterized in that in the first oxidation step
a base with a pKa value of from 7.5 to 13.0, preferably selected from the group consisting of phosphates, carbonates and mixtures thereof, most preferably selected from Na3PO4, Na2HPO4 and mixtures thereof, is employed.
 
4. A process according to any of the preceding claims, characterized in that the water content of said solution before the first oxidation step is from 1% to 80%, preferably 30% to 50%.
 
5. A process according to any of the preceding claims, characterized in that the extraction solvent for the extraction step is selected from the group consisting of ethylacetate, trichloromethane and mixtures thereof.
 
6. A process according to any of the preceding claims, characterized in that the oxidizing agent for said first oxidation step or said second oxidation step or for both oxidation steps is selected from the group of oxygen or air.
 
7. A process according to any of the preceding claims, characterized in that in said first oxidation step parts of the HMF remain unreacted and/or are oxidized to 2,5-diformylfuran (DFF) and that in said extraction step said unreacted HMF and/or said DFF are extracted from said first reaction mixture.
 
8. A process according to claim 7, characterized in that said extracted unreacted HMF and/or said extracted DFF are recycled to the solution before the first oxidation step.
 
9. A process according to any of the preceding claims characterized in that after the extraction step the extraction solvent and the high boiling polar solvent are separated from each other.
 


Ansprüche

1. Verfahren zur Herstellung von 2,5-Furandicarbonsäure (FDCA) durch Oxidation von 5-Hydroxymethyl-2-furfural (HMF), wobei das HMF in einer Lösung in einem aprotischen hochsiedenden polaren Lösungsmittel und Wasser vorliegt, gekennzeichnet durch die Kombination von

- einem ersten Oxidationsschritt, bei dem das HMF in der Lösung zumindest teilweise oxidiert wird, um ein erstes Reaktionsgemisch zu ergeben, umfassend mindestens eine Monosäure, die ausgewählt ist aus der Gruppe, bestehend aus 5-Hydroxymethylfuran-2-carbonsäure (HMFA) und 5-Formylfuran-2-carbonsäure (FFCA), und gegebenenfalls FDCA,

- einem Extraktionsschritt nach dem ersten Oxidationsschritt, bei dem das aprotische hochsiedende polare Lösungsmittel mittels eines Extraktionslösungsmittels aus dem ersten Reaktionsgemisch extrahiert wird, wobei die mindestens eine Monosäure in einer wässrigen Phase verbleibt,

- einem zweiten Oxidationsschritt, bei dem die zumindest eine Monosäure zu FDCA oxidiert wird.


 
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das hochsiedende aprotische polare Lösungsmittel aus der Gruppe, bestehend aus Dimethylsulfoxid (DMSO), N-Methyl-2-pyrrolidon (NMP), N,N-Dimethylformamid (DMF) oder N,N-Dimethylacetamid (DMA) und Gemischen davon, ausgewählt ist.
 
3. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in dem ersten Oxidationsschritt
eine Base mit einem pKa-Wert von 7,5 bis 13,0 verwendet wird, bevorzugt ausgewählt aus der Gruppe, bestehend aus Phosphaten, Carbonaten und Gemischen davon, am meisten bevorzugt ausgewählt aus Na3PO4, Na2HPO4 und Gemischen davon.
 
4. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Wassergehalt der Lösung vor dem ersten Oxidationsschritt 1% bis 80%, vorzugsweise 30% bis 50%, beträgt.
 
5. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Extraktionslösungsmittel für den Extraktionsschritt aus der Gruppe, bestehend aus Ethylacetat, Trichlormethan und Gemischen davon, ausgewählt ist.
 
6. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Oxidationsmittel für den ersten Oxidationsschritt oder den zweiten Oxidationsschritt oder für beide Oxidationsschritte aus der Gruppe aus Sauerstoff oder Luft ausgewählt ist.
 
7. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in dem ersten Oxidationsschritt Teile des HMF unumgesetzt bleiben und/oder zu 2,5-Diformylfuran (DFF) oxidiert werden und dass in dem Extraktionsschritt das unumgesetzte HMF und/oder das DFF aus dem ersten Reaktionsgemisch extrahiert wird bzw. werden.
 
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass das extrahierte unumgesetzte HMF und/oder das extrahierte DFF vor dem ersten Oxidationsschritt in die Lösung zurückgeführt wird bzw. werden.
 
9. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Extraktionslösungsmittel und das hochsiedende polare Lösungsmittel nach dem Extraktionsschritt voneinander getrennt werden.
 


Revendications

1. Procédé de production d'acide 2,5-furandicarboxylique (FDCA) par oxydation de 5-hydroxyméthyl-2-furfural (HMF), ledit HMF étant présent dans une solution dans un solvant polaire aprotique à point d'ébullition élevé et de l'eau, caractérisé par la combinaison

- d'une première étape d'oxydation, où le HMF est au moins partiellement oxydé dans ladite solution pour obtenir un premier mélange réactionnel comprenant au moins un monoacide choisi dans le groupe constitué par l'acide 5-hydroxyméthylfurane-2-carboxylique (HMFA) et l'acide 5-formylfurane-2-carboxylique (FFCA), et facultativement le FDCA,

- d'une étape d'extraction après la première étape d'oxydation, où ledit solvant polaire aprotique à point d'ébullition élevé est extrait dudit premier mélange réactionnel au moyen d'un solvant d'extraction, où ledit au moins un monoacide reste dans une phase aqueuse,

- d'une seconde étape d'oxydation, où ledit au moins un monoacide est oxydé en FDCA.


 
2. Procédé selon la revendication 1, caractérisé en ce que le solvant polaire aprotique à point d'ébullition élevé est choisi dans le groupe constitué par le diméthylsulfoxyde (DMSO), la N-méthyl-2-pyrrolidone (NMP), le N,N-diméthylformamide (DMF) ou le N,N-diméthylacétamide (DMA) et des mélanges de ceux-ci.
 
3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que dans la première étape d'oxydation
une base avec une valeur pKa de 7,5 à 13,0, de préférence choisie dans le groupe constitué par des phosphates, des carbonates et des mélanges de ceux-ci, de la manière la plus préférée choisie parmi Na3PO4, Na2HPO4, et des mélanges de ceux-ci, est utilisée.
 
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur en eau de ladite solution avant la première étape d'oxydation est de 1 % à 80 %, de préférence de 30 % à 50 %.
 
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le solvant d'extraction pour l'étape d'extraction est choisi dans le groupe constitué par l'acétate d'éthyle, le trichlorométhane et des mélanges de ceux-ci.
 
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent oxydant pour ladite première étape d'oxydation ou ladite seconde étape d'oxydation ou pour les deux étapes d'oxydation est choisi dans le groupe de l'oxygène ou de l'air.
 
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que dans ladite première étape d'oxydation, des parties du HMF restent sans avoir réagi et/ou sont oxydées en 2,5-diformylfurane (DFF), et en ce que dans ladite étape d'extraction, ledit HMF n'ayant pas réagi et/ou lesdits DFF sont extraits dudit premier mélange réactionnel.
 
8. Procédé selon la revendication 7, caractérisé en ce que ledit HMF n'ayant pas réagi extrait et/ou ledit DFF extrait sont recyclés dans la solution avant la première étape d'oxydation.
 
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'après l'étape d'extraction, le solvant d'extraction et le solvant polaire à point d'ébullition élevé sont séparés l'un de l'autre.
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description