MXPA97004215A - Method for selectively preparing 2.5-furandicarboxaldehödo from 5-hydroxymethyl-furan-2-carboxaldeh - Google Patents

Abstract

The present invention relates to: a process for the selective manufacture of 2.5 furandicarboxaldehyde (FDC) from 5-hydroxymethyl-furan-2-carboxaldehyde (HMF) dissolved in a liquid solvent, in contact with at least one of a metal selected from metals of groups IVB, VB and VIB of the Periodic Table of Elements, at a temperature of 75 to 200

Description

METHOD FOR SELECTIVELY PREPARING 2,5-FURANDICARBOXALDEHYDE FROM 5-HYDROXYMETHYL-FURAN-2-CARBOXALDEHYDE FIELD OF THE INVENTION The invention consists of a process for the selective manufacture of 2, 5-furandicarboxaldehyde (FDC) from hydroxymethyl-furan- 2-carboxaldehyde (HMF). The HMF can be synthesized from substances of vegetable origin that contain or that can release fructose or polyfructans, for example topinambur extract. HMF is a starting product in the synthesis of many furanic derivatives that can be used in turn to produce polymers with interesting properties (possibility of particular chemical modifications, resistance to temperature and fire, chemical inertness, mechanical properties and / or special electrical and others). BACKGROUND OF THE INVENTION Among the numerous derivatives of HMF, FDC is a monomer that can have many applications. In particular it can serve: for the synthesis of some polymers and macrocycles, especially in the pharmaceutical branch; as a crosslinking agent in the preparation of special polymers; to agglutinate the sand in the foundries; for the manufacture of the layer that separates aqueous solutions from alkaline batteries; as an anticorrosive agent; as a surface treatment agent for metals such as copper, nickel; as an intermediary in the synthesis of other symmetric or asymmetric furanic compounds such as furan-2, 5-dicarboxylic acid (FDA). However, the FDC is not manufactured industrially because there is no cost-effective procedure that can be applied continuously and under conditions compatible with current requirements of respect for the environment. The known FDC synthesis procedures are the stoichiometric reactions (which have the disadvantage of being very polluting, causing corrosion in the facilities, being expensive and very difficult to perform continuously), or reactions in homogeneous catalysis (which are very difficult to perform in an uninterrupted manner and require separation of dissolved reactive products). The oxidation reactions of HMF in heterogeneous catalysis present difficulties a priori, insofar as the HMF is not stable at the high temperatures required to activate the solid catalysts of oxidation, since its degradation occurs from 100 ° C. However, the oxidation of HMF in a liquid medium in heterogeneous catalysis has already been described. For example, DE-A-3,826,073 proposes the use of platinum on activated carbon as a catalyst at a temperature of 70 ° C to oxidize an aqueous solution of HMF. The reaction is not selective in FDC (the yield in FDC is 24%) and also produces formyl-5-furan carboxylic acid-2 (FFCA) and furan-dicarboxylic acid2, 5. Also, the publication "Platinium Catalyzed Oxidation of 5-hydroxymethylfulfural "P. VINKE, HE van DAM, H. van BEKKUM, New Delopments in Selective Oxidation, G. GENTI and F.TRIFIRO Editeur, Elsevier Science Publishers, Amsterdam, Studies in Surface Science and Catalysis, 1990, 55, p. 147-156, describes an oxidation reaction of HMF in an aqueous medium catalyzed by platinum on alumina at 60 ° C in the presence of oxygen. The reaction produces very little FDC and above all is indicated to selectively manufacture the FFCA. SUMMARY OF THE INVENTION On the other hand, many syntheses of aldehydes from alcohols in heterogeneous catalysis are known from the prior art. In all these reactions, an infinite number of catalysts were used: most of the crude or supported metal oxides (iron, copper, zinc, silver, nickel, cobalt, magnesium, vanadium, zirconium, molybdenum, bismuth, antimony), silica, the silicates, the zeolites. In most cases these reactions occur in the gas phase at high temperature (more than 200 ° C). Therefore, all these reactions can not a priori be transposed to the oxidation of the HMF because their thermal instability causes the reaction to develop in the liquid phase and at low temperature (less than 200 ° C). In every request the terms selectivity, conversion and performance are used referring to the following definitions; where C designates the conversion, S the selectivity and R the yield: amount of transformed HMF X 100 c (%) = - amount of initial HMF ,. amount of FDC formed S (%) = X 100 amount of HMF transformed , amount of FDC formed R (%) = SXC / 100 = X 100 amount of initial HMF DETAILED DESCRIPTION OF THE INVENTION In this context, the present invention refers to a method of selective manufacture of the FDC from the HMF with qualities that allow its industrial exploitation (low pollutant, easy to apply in an uninterrupted manner, fast, inexpensive and good performance) . In this regard, it should be noted that both the selectivity and the conversion of the process are essential to facilitate or even avoid the subsequent stages of separation or purification which are generally costly. Also, the invention aims at a process whose performance in FDC is greater than 60% and whose conversion and selectivity are greater than 90%. In this sense, the invention deals with a method of selective manufacture of the FDC from the HMF in liquid phase and at low temperature (less than 200 ° C). In a process according to the invention, the dissolved HMF is placed in a liquid solvent in contact with at least one solid compound comprising at least one metal selected from the metals of columns IV B, VB and VI B of the periodic classification of the elements and is placed in reaction medium at a temperature between 75 ° C and 200 ° C. Among the metals that can be used, mention may be made in particular of titanium, zirconium, vanadium, niobium, chromium, molybdenum and tungsten. These metals can be used in pure metallic form or as a salt or, preferably, in simple or mixed oxides. In addition, these metals can be used in the mass state (ie not supported) or instead on a support. In the latter case, the support may also contain a metal or be formed of a silicate, especially a tectosilicate or a clay.

Advantageously, at least one solid compound comprising vanadium oxide is used. Indeed, clearly improved results have been obtained, and surprisingly, with the vanadium oxide V205. According to the invention, the reaction is carried out in the presence of oxygen, especially in a reactor in which a gas pressure consisting of oxygen is maintained. Advantageously and according to the invention, the reaction is carried out in a reactor in which an air pressure of between 5,105 Pa and 30,105 Pa is maintained. Oxygen allows permanent regeneration of the vanadium oxide, which simultaneously acts as an oxidant and of solid catalyst. More precisely, a sufficient partial pressure of oxygen is maintained to keep the vanadium oxide at an optimum oxidation level for the reaction. The solid compound can consist of vanadium oxide in unsupported free state (in the form of a mass). In this case, the reaction is preferably carried out at a temperature higher than 150 ° C, especially of the order of 170 ° C. However, in an advantageous manner and according to the invention, the vanadium oxide supported on a metal oxide support of the amphoteric type with predominance of acid is used as a solid compound. Indeed, it has been possible to demonstrate a synergy effect between vanadium oxide and its metal oxide support, especially when the latter is neither acid, nor basic, nor amphoteric with basic predominance. In particular and according to the invention, vanadium oxide supported on a titanium oxide support is used. Advantageously and according to the invention, the titanium oxide support is formed from titanium oxide comprising between 50 and 100% of anatase phase and between 50% and 0% of rutile phase, more particularly between 60% and 75% of anatase phase and between 40% and 25% of rutile phase, particularly of the order of 64% of anatase phase and of the order of 36% of rutile phase. Under these effective conditions, the reaction can be carried out at a very low temperature, below 100 ° C, especially of the order of 90 ° C, obtaining a conversion a selectivity both higher than 90%. The yields of the process according to the invention also depend on the weight ratio of the vanadium in the solid compound. Advantageously and according to the invention, a solid compound is used that includes between 1% and 56% and more particularly more than 4% by weight of vanadium. Good results were obtained for a weight ratio of vanadium in the solid compound comprised between 7% and 7.5%, especially of the order of 7.33%. Furthermore, the solid compound is used according to a mass ratio with respect to the initial amount of HMF comprised between 0.5 and 5, especially of the order of 2. According to the invention, the HMF is placed in a liquid polar solvent suitable for solubilization in HMF. and so that it remains chemically inert at the reaction temperature and against the solid compound. According to the invention, the polar solvent must also be suitable for solubilizing FDC. According to the invention, the solvent is advantageously an aromatic solvent or a ketone. Advantageously and according to the invention, methyl isobutyl ketone (MIBC) can be used as a solvent. This solvent is all the more advantageous in that the HMF generally leaves a synthesis, in a condition dissolved in MIBC. According to the invention, the reaction is then carried out with a starting HMF concentration that is higher than 6.10"2 moles per liter and an air pressure higher than 5,105 Pa, particularly in the order of 10,105 Pa. Advantageously and in accordance with the invention also toluene can be used as a solvent In this case and according to the invention, the reaction is carried out with a starting HMF concentration comprised between 2.10"2 and 8.10" 2 moles per liter and an air pressure higher than 10.105 Pa, especially in the order of 16,105 Pa. In the following examples the reactions were carried out in a closed reactor of 100 ml equipped with an internal rotary stirrer with its magnetic transmission by turbine and which is equipped with a channel for the entrance of gas under pressure and a Extraction channel, consisting of heating and equipped with a temperature regulation.The HMF used, with a purity greater than 99%, is a light yellow solid, with It is molar equal to 126.11 g, which melts at 35 ° C. The FDC is a straw yellow solid with a molar mass equivalent to 124 g and having an absorption wavelength in ultraviolet rays of 280 nm. The predetermined amount of HMF is pre-dissolved in 50 ml of the selected solvent and then introduced with the solid catalyst into the reactor. After a period of agitation, an extraction is carried out which allows to accurately dose the initial amount of HMF in the reactor. The reactor is then heated under stirring at 1000 revolutions per minute up to the selected reaction temperature, the reaction time being counted from obtaining this temperature. The doses of HMF and FDC are carried out by chromatography: HPLC at 15 minutes, 30 minutes, 60 minutes, 90 minutes, 150 minutes and 240 minutes of reaction time. When the solvent used is toluene, the chromatography column is a monosaccharide H + column. The sample used is furfural and the elution solvent is an aqueous solution of trifluoroacetic acid. When the solvent used is MIBC, the chromatography column is a column containing an inserted support. The sample used is hydroquinone and the eluting solvent is a mixture of cyclohexane (80%), dichloromethane (16%) and isopropanol (4%). EXAMPLE 1 In this example, the vadium oxide V205 (unsupported) is used with a ratio of the mass of the solid compound V205 to the HMF introduced into the reactor equal to 2. The weight ratio of vanadium in the V205 is 56. This catalyst is previously calcined for 4 hours at 500 ° C, the air pressure is 10,105 Pa, the temperature of 170 ° C and the solvent is toluene. First the thermal stability of the HMF at 170 ° C is tested by introducing it without catalyst dissolved in toluene. After 90 minutes a 10% loss of HMF is noted. In the presence of a catalyst, the selectivities obtained are of the order of 70% with a conversion greater than 90%. After 90 minutes of reaction, the conversion is 91%, and the selectivity is 69%, that is, there is a 62% yield. EXAMPLE 2 The same test as in Example 1 is carried out by replacing the free vanadium oxide with the vanadium oxide on a support of titanium oxide in the anatase phase. To prepare this catalyst: 5 g of titanium oxide are wetted in anatase form in distilled water and dried in the oven for 20 hours at 100 ° C; Add to 560 mg of NHV0 to a solution of 20 ml of oxalic acid ÍM and the mixture is heated to an intense blue color; this solution is added to the support and stirred for 30 minutes, then evaporated and dried in the oven at 100 ° C; the catalyst is crushed immediately, passed through a sieve and allowed to calcinate for 5 hours at 450 ° C. The catalyst analysis shows that the 8. 17% of its weight is vanadium (centesimal analysis) and it has a specific surface area of 9m2 / g (Brunauer-Emett-Teller method, isotherms of nitrogen absorption). The selectivities obtained fluctuate between 60 and 70%, with a conversion greater than 90% after only minutes of reaction. Therefore, the transformation kinetics is faster. After 20 minutes, the conversion is 95% and the selectivity is 67%. The yield obtained is 64%. EXAMPLE 3 First, the solid compounds formed by vanadium oxide are prepared on a support * of titanium oxide containing 64% in the anatase phase and 36% in the rutile phase. 10 g of this Ti02 support, containing 64% in the anatase phase and 36% in the rutile phase (indicated with the Ti02 (A / R), partially dehydroxylated (TiOH) series in a 250 ml solution of water in the presence of of an amount varying between 0.23 and 4.56 g of ammonium metavanadate (NHV03), concentrated hydrochloric acid is added to ph 2, the mixture is stirred for 24 hours and then centrifuged to remove the floating particles. wash several times in hot water (70 ° C-100 ° C) to remove the elements that did not react After each wash, the mixture is centrifuged to remove the floating particles, the catalyst is immediately recovered, dried in the oven ( 60 ° C), it is crushed, passed through a sieve (diameter of 0.063 to 0.125 mm) and calcined for 4 hours under an air flow at 500 ° C.

By varying the amount of initial NHV03, Cl to C6 catalysts containing different proportions of vanadium oxide are obtained. The centesimal analysis allowed dosing the amount of vanadium of the catalyst and of the active phase V205. in relation to the Ti02 support The specific surface of the catalysts was also determined by the Brunauer-Emett-Teller method of the nitrogen absorption isotherms.

Then the different catalysts V205 with Ti02 will be designated with the reference (Cl to C6) indicated in the previous table. The same test was carried out as in Example 1 (170 ° C) replacing V205, without support by the catalyst C5 (V205 on Ti02 (A / R) at 7.33% vanadium). The selectivities obtained are between 70 and 80% with a conversion of 80% provided that the duration of the reaction is greater than or equal to 90 minutes. For a duration of 90 minutes, the conversion is 80% and the selectivity is 77%. EXAMPLE 4 The same test was carried out as in Example 3, but at a temperature of 90 ° C, with an air pressure of 16. 105 Pa and with the following catalysts: C5 (7.33% vanadium), Ti02 (A / R) alone (0% vanadium) V205 without support (56% vanadium) and V205, on Ti02 100% anatase (8.17% vanadium). With the V205 without support, the selectivities obtained are between 75% and 80%, but the conversion is still less than 30%. At that temperature the yield is less than 25%. With the support Ti02 (A / R) only the selectivities obtained are greater than 94% but the conversion is less than 15%, therefore, the yield is lower than the 14% With V20 on Ti02 100% anatase, the selectivities obtained vary between 75 and 90% with a conversion of less than 40%. After 240 minutes the maximum yield is 31%. With V20 on Ti02 (AR) the selectivities and the investments obtained, therefore, the yields, are frankly superior. Thus, after 60 minutes of reaction, the yield is higher than 66%. After 90 minutes the conversion is 81% for a result of 97% and a yield of 79%. After 30 minutes of reaction, the selectivities are higher than 80% and the conversions are 54%. At 90 ° C, a synergistic effect between V205 and Ti02 support (A / R) (64% anatase and 36% rutile). EXAMPLE 5 The selectivities obtained are then compared with the other catalysts V205 / Ti02 (A / R) of different weight proportions of vanadium. The tests were carried out under the conditions of Example 4, first with toluene and then with MIBC, with a mass ratio of the catalyst on MHF of 2 (0.4 g of catalyst for 0.2 g of HMF in 50 ml of solvent) . Conversions and selectivities were also determined, that is, the yields for reaction times of 1 and 4 hours.

When plotting the curves corresponding to these tables, it is shown that in the monolayer there is a proportion of vanadium higher than 4%.

EXAMPLE 6 With the catalyst C5 (7.33% vanadium) the influence of the mass of the catalyst for the conversion of the HMF and the selectivity of FDC was evaluated, first in the toluene and then in the MIBC, under the conditions of example 4. - lí EXAMPLE 7 With 0.4 g of C5 catalyst (7.33% vanadium), the influence of the initial amount of HMF on the conversion and the selectivity of FDC, in toluene and MIBC, in 50 ml and in the conditions of the example 4 EXAMPLE 8 The influence of air pressure with catalyst C5 (V205 on Ti02 (A / R) at 7.33% vanadium) was evaluated at 90 ° C, with the mass reaction of the catalyst on the substrate of 2 (0.4 g of catalyst for 0.2 g of HMF), in toluene and then in MIBC. The air pressure was varied from 0 to 26,105 Pa.

EXAMPLE 9 The influence of temperature between 75 ° C and 110 ° C, under the same conditions as example 8, fixing the air pressure at 16.105 Pa.

From these tests it follows that the oxidation reaction of HMF in FDC in liquid medium has a selectivity and a satisfactory yield at low temperature (less than 200 ° C) in the presence of vanadium oxide. In particular vanadium oxide on titanium oxide, having between 60 and 75% (especially 64%) of anatase phase and between 40 and 25% (especially 36%) of rutile phase, at 90 ° C, it produces a synergistic effect between the active phase and the support (example 4) and a selectivity of 97% for a yield of 79% in 90 minutes. If the proportion by weight of vanadium is varied between 1.19 and 8.6%, the yield remains higher than 70% and the selectivity will be higher than 78% at 90 ° C (example 5). Between 1.67 and 7.33%, the yield is higher than 84% and the selectivity higher than 92% in toluene. With an 8.6% vanadium, the conversion is total and the selectivity is 78%. In examples 6 and 7 it is shown that the mass ratio of the catalyst on the HMF can vary 0.5 and 5 and give good results, although the best results are obtained with a ratio of 2. When the initial concentration of HMF is higher than 3 , 14.10 ~ 3 moles per 50 ml, that is, around 6.10 ~ 2 moles / 1, it is preferable to use the MIBC (example 7). On the contrary, if that concentration is less than 3.88.10 ~ 3 moles per 50 ml, that is, about 8.10"2 moles / 1, it is preferable to use toluene, and in example 8 it is shown that the conversion is almost changes (75-80%) from 16,105 Pa of air in toluene In the MIBC the maximum conversion (35-40%) is reached from 10,105 Pa of air Finally, in example 9 it is shown that at 75 ° C the conversion is not very large, that at 90 ° C the conversion and the selectivity are good and that the selectivity in the MIBC decreases at 110 ° C. From these results the industrial production of the FDC can be considered continuously, by one or several stages in a multiple contact reactor, especially of the pulsed column type, from the HMF in liquid phase at 90 ° C in the presence of V205, supported by Ti02 with 64% anatase phase and 36% of rutile phase, with 7.3% vanadium Among the other oxides or metal salts that can be used we can mention the oxide s or salts of titanium, zirconium, vanadium, niobium, chromium, molybdenum and tungsten. The oxides or metal salts can be used in the mass state (without support) or with support.

Claims (12)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore the property described in the following claims is claimed as property. A process for producing 2,5-furandicarboxaldehyde (FDC) from 5-hydroxymethyl furan 2-carboxaldehyde (HMF) in liquid medium, characterized in that the MHF dissolved in a liquid solvent is contacted with a solid compound having at least one metal oxide chosen from the metals of columns IV B, VB and VI B of the periodic table of classification of the elements, and that reaction medium is set at a temperature between 75 ° C and 200 ° C.
2. 2. A process according to claim 1, characterized in that a solid compound containing vanadium oxide is used.
3. 3. A process based on claim 2, characterized in that a solid compound consisting of unsupported vanadium oxide is used.
4. 4. A process according to claim 2, characterized in that the vanadium oxide is used as a solid compound on a metal oxide support of the amphoteric type with predominance of acid.
5. 5. A process according to claim 4, characterized in that the vanadium oxide is used on a titanium oxide support.
6. 6. A process according to claim 5, characterized in that the titanium oxide support has between 50 and 100% anatase phase and between 50 and 0% rutile phase.
7. 7. This method, according to claim 6, is characterized in that the titanium oxide support has between 60 and 75% anatase phase and between 40 and 25% rutile phase.
8. 8. A process according to claim 7, characterized in that the titanium oxide support has a 64% anatase phase and a 36% rutile phase.
9. 9. A process according to claims 6, 7 and 8, characterized in that the reaction is carried out at a temperature below 100 ° C, in particular at 90 ° C.
10. 10. This process according to claims 2, 3, 4, 5, 6, 7, 8 and 9, characterized in that a solid compound having between 1 and 56% by weight of vanadium is used.
11. 11. A process according to claim 10, characterized in that a solid compound having at least 4% by weight of vanadium is used.
12. 12. This process according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, characterized in that the solid compound is used according to a mass ratio between 0.5 and 5, in particular of 2, according to the initial amount of HMF.