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    • 专利摘要:
    Procedure for the oxidation of furfural to maleic acid. The object of the present invention is a method for obtaining maleic acid from furfural. The process is based on the treatment of the liquid phase furfural with an oxidizing agent, particularly hydrogen peroxide, in the presence of at least one catalyst. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2558261A1
    申请号:ES201431169
    申请日:2014-07-31
    公开日:2016-02-02
    发明作者:Noelia ALONSO FAGÚNDEZ；Manuel LÓPEZ GRANADOS；Rafael MARISCAL LÓPEZ
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    5 SECTOR OF THE TECHNIQUE AND OBJECT OF THE INVENTION
    The present invention falls within the scope of catalysis. The use of heterogeneous catalysts versus homogeneous catalysts is of remarkable importance in a chemical process, because the subsequent operations of
    10 separation that would imply possible reuse. The object of the present invention is a process for carrying out the oxidation of furfural in liquid phase with hydrogen peroxide as an oxidizing agent in the presence of a titanium silicate as a catalyst, obtaining as main product maleic acid.
    15 STATE OF THE TECHNIQUE
    Both maleic acid (AM) and its anhydrous form are chemical intermediates that find application in many fields of the chemical industry. They are used as raw materials in the synthesis of unsaturated polyester resins, coatings
    20 superficial, lubricant additives, plasticizers and copolymers. They are also used to obtain fertilizers and agrochemicals. The hydrogenation of AM with metal catalysts of Pd / C and Zn / Hg results in the synthesis of succinic acid, an important "building block:" used as an additive in fuels, solvents, biopolymers, plasticizers and fine chemistry.
    25 Maleic anhydride can be synthesized industrially by selective oxidation of n-butane or benzene. Due to the environmental problems associated with benzene, as well as its high toxicity, it has been progressively replaced by n-butane as a raw material, a product that is more environmentally friendly and cheaper. AM is
    30 finally obtained by heating the maleic anhydride in water. This described production method implies the dependence of oil as a starting product for obtaining the AM, with the consequent problems associated with its supply, its continuous price increase and its contaminating character. Furfural is used in this work as a raw material for the synthesis of AM. The furfural is
    35 obtained from the acid dehydration of xylose, a monosaccharide that is part of

    the composition of biomass ("Biorefining: Heterogeneously Catalyzed Reactions of Carbohydrates for the Production of Furfural and Hydroxymethylfurfuraf ', R. Karinen et al., ChemSusChem 4 (2011) 1002-1016]. Furfural is a product used today as a solvent, in the manufacture of resins or artificial fibers and gums, as well as fuel and lubricant additive and for the synthesis of furfuryl alcohol, furoic acid and
    Furan.
    Several research groups have worked on the oxidation of furfural both in the gas phase and in the liquid phase. The oxidation of furfural in the gas phase results in the obtaining of maleic anhydride, using oxygen as an oxidizing agent. Temperatures above 250 "C are required with catalysts based on vanadium oxides, yields around 75% (" Selective conversion of furfural to
    maleic anhydride and furan with VOxlAI20 3 catalysts "Alonso-Fagúndez, N. et al. ChemSusChem 5 (2012) 1984-1990].
    The oxidation reaction of furfural in liquid phase to produce AM can be performed using oxygen or hydrogen peroxide as oxidizing agents. In the first case, phosphomolibic acid has been used as a catalyst in a two-phase water / tetrachloroethane system, yielding 35% ("Catalytic aerobic oxidation of renewable furfural with phosphomolybdic acid catalyst: An alternative route to maleic acid"
    Guo, H. et al. Journal 01 Physieal Chemistry C 35 (2011) 17516-17522].
    Oxidation of furfural with hydrogen peroxide has been performed using H2S04 as
    catalyst, with succinic acid being the main product, with a yield of around 45%. In addition, other products such as maleic acid, succinic acid, fumaric acid, 2 (5H) -furanone or 5-hydroxy-2 (5H) -furanone are also produced, which gives an idea of the existence of a very complex reaction mechanism. To improve the yield to AM it is necessary to increase the molar ratio H20 2 / furfural ["Polystyrene sulphonic acid: An acid catalyst from polystyrene waste for reactions of interest in biomass valorization'1. N. Alonso-Fagúndez et al. Catalysis Today 234 ( 2014) 285-294).
    Heterogeneous catalysis is always more interesting, because the recovery tasks of the reaction medium catalyst are facilitated for later reuse. There are several works in this regard in which acid catalysts such as Amberlite 15, ZSM-5, polystyrenesulfonic acid or p-toluenesulfonic acid with a molar ratio H20 2 / furfural of 4 and a temperature of BO "C (" Highly efficient aqueous are used oxidation of furfural 3
    P201 431169 07-31-201 4
    to succinic acid using reusable heterogeneous acid catalyst with hydrogen peroxide "
    Choudhary, H. et al. Chemistry Letters 41 (2012) 409-411; "Metal-free oxidative synthesis of succinic acid from biomass-derived furan compounds using a solid acid catalyst with hydrogen peroxide" Choudhary, H et al. Applied Catalysis A: General 458 (213) 55-62; "Polystyrene sulphonic acid: An acid catalyst from polystyrenewaste for reactions of interest in biomass valorization", N. Alonso-Fagúndez et al. Catalysis Today 234 (2014) 285-294).
    The proposed reaction mechanism for the oxidation of furfural towards AM with acid catalysts is the one represented in scheme 1 ["Oxidation of furans
    (Review) "Badovskaya, L.A. and Povarova, L. V. Chemistry of Hetocyclic compounds 45 (2009) 1023-1034).
    In the reaction shown in the scheme of Figure 1, oxidation of furfural to 2-hydroxyfuran and formic acid occurs first, in a Baeyer-Villiger reaction. 2-Hydroxyfuran is in equilibrium with 2- (5H) -furanone and 2- (3H) -furanone. From the oxidation of 2 (5H) -furanone, 5-hydroxy-2 (5H) -furanone is obtained, which is in equilibrium with p-formylacrylic acid. Finally, oxidation of p-formylacrylic acid results in maleic acid. From the oxidation of ¡3-formylpropionic acid derived from 2 (3H) -furanone, succinic acid is finally obtained. According to this reaction mechanism, two moles of H20 2 are required per mole of furfural to obtain succinic acid and
    of three moles of H20 2 per mole of furfural to obtain maleic acid.
    The titanium silicalite catalyst (TS-1) has been widely used for various hydrocarbon oxidation reactions: for the hydroxylation of aromatic compounds ["Hydroxylation of phenol with hydrogen peroxide on EUROTS-1 catalyst" Martens, J. A. and col. Applied Catalysis A: General 99 (2003) 71-84], for the epoxidation of alkenes
    ["Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite" Clerici, M. G. Y col. Journal of Catalysis 129 (1999) 159-167], for the amoxidation of cytohexanone ('' Ammoximation of CycJohexanone to Cyclohexanone Oxime Catalyzed by Titanium SiJicalite-1 Zeolite in Three-phase System "Liu, G. et al. Chinese Journal of Chemical Engineering 20 (2012) 889-894] And for the oxidation of alkenes and alcohols ["Oxidation of Alcohols with H20 Z Catalyzed by Titanium SilicaJite-1" Maspero, F. and Romano,
    or. Journal 01 Catalysis 146 (1994) 476-482].
    In recent publications, titanium silicalite 1 (TS-1) has been used as a catalyst
    for oxidation of furan under mild conditions using H20 2 as an oxidant ['Titanium
     31-07-201 4
    silicaJite 1 (TS-1) catalyzed oxidative transformations of furan derivatives with hydrogen peroxide "Wahlen, J. et al. Advanced synthesis and catalysis 346 (2004) 333-338; '~ n efficient synthesis of 5-hydroxy-2 (5H) -furanone: Using a titanium silicate molecular sieve catalystU Kumar, P. et al. Green Chemistry 2 (2000) 29-31) Furan, which could be obtained from the furfural, is an aromatic heterocycle with 4 C atoms and one of 0, chemically similar to furfural, which has 5 carbon atoms because it also contains an aldehyde group attached to the fury ring.Depending on the temperature of the reaction and the amount of H20 2 used, the products obtained from the furan were maleic dialdehyde to a temperature of 25 ° C and a molar ratio H20 2 / Furan of 1.25, or 5hydroxy-2 (5H) -furanone for a temperature of ooe and a molar ratio H20 2 / Furan of 2.4 The two compounds with 4 mentioned e atoms, maleic dialdehyde and hydroxyfuranone, could ox go to AM in the presence of hydrogen peroxide so that the furan could be used to obtain AM. In the process object of the present invention it is proposed to use TS-1 as a catalyst to perform the oxidation but directly from furfural (a compound with 5 atoms of e) to AM using H20 2. For this oxidation to occur it is necessary in the practice that the TS-1 is able to remove a carbon atom, in addition to performing the corresponding oxidation stages.
    EXPLANATION OF THE INVENTION
    The object of the present invention is a process for the oxidation of furfural to maleic acid with an oxidizing agent that is carried out with at least titanium silicalite as a catalyst.
    In a preferred embodiment of the invention: the oxidizing agent is hydrogen peroxide. -the molar ratio between the oxidizing agent and the furfural is between 4 and 15 -the initial concentration of furfural in the reaction medium is between 2 and 10% by weight -the reaction temperature is between 5 and 70 oC
    In one embodiment of the process of the invention, titanium silicalite is used as the sole catalyst, the mass ratio between the furfural and the titanium silicalite being between 0.5 and 4. In another embodiment of the invention at least a second is used. catalyst in addition to titanium silicalite

    Preferably, the process object of the invention comprises the following steps:
    - contacting the reaction medium comprising furfural and the oxidizing agent with the titanium silicalite catalyst for a period of time between 1 and 24 hours - isolating the catalyst from the reaction medium by centrifugation or filtration More preferably, the isolated catalyst it is reused at least once by contacting it with the reaction medium comprising furfural and the oxidizing agent and then isolating it from the reaction medium. Even more preferably, the catalyst is reused and isolated between 1 and 6 times. In a particular embodiment, the catalyst is isolated by membrane filtration. In another alternative embodiment, the process object of the invention comprises the following steps: - contacting the reaction medium comprising furfural and the oxidizing agent in a molar ratio oxidizing agent / furfural between 2 and 3 with the catalyst of titanium silicalite for a period of time between 2 and 10 hours to obtain 5-hydroxyfuranone - isolate the titanium silicalite catalyst from the reaction medium by centrifugation or filtration - contact the 5-hydroxyfuranone with the oxidizing agent in a ratio molar initial oxidizing / furfural agent comprised between 1 and 3 in the presence of an acid catalyst with sulfonic groups for a period of time between 24 and 48 hours to obtain maleic acid. Preferably, the oxidizing agent is hydrogen peroxide. In a particular embodiment of this alternative embodiment of the process of the invention: the step of obtaining 5-hydroxyfuranone is carried out with a stoichiometric ratio between hydrogen peroxide and furfural of 2.4 and during a period of 4 hours -the isolation of the titanium silicalite catalyst is carried out by filtration. -the acid catalyst with sulfonic groups is Amberlyst 70 -the step of obtaining maleic acid is carried out with a molar ratio between hydrogen peroxide and equivalent initial furfural of 2 for a period of 24 hours

    BRIEF DESCRIPTION OF THE FIGURES
    In the legend of the figures the following nomenclature is used:
    Ae. Maleieo (AM); Ae. Succinieo (AS); Ae. Formic (AF);5-hydroxy-2 (5H) -luranone (5-hydrox.); 2 (5H) -Furanone (5-luran.);Ae. Fuming (AFum); Ae. Málieo (AMa); Ae. Furoieo (AFur);
    Figure 1: Scheme of the reaction mechanism of oxidation of furfural to AM with acid catalysis.
    10 Figure 2: Temperature effect. Reaction conditions: 4.6% in furfural weight; 2.3% by weight TS-1; H20 2 / F = 7.5 (.) Furfural conversion; (e) AM performance; C "') AMa yield; (. &) AF yield; (O) 5-hydroxyfuranone yield).
    15 Figure 3: Effect of the H20 2 / F molar ratio. Reaction conditions: 4.6% in furfural weight; 323 K; 2.3% by weight TS-1. (.) fuñural conversion; (e) AM performance; C'9 ') AMa yield; (. &) AF performance; (O) 5-hydroxyfuranone yield).
    Figure 4: Effect of the TS-1 / Furfural mass ratio. "A) 0% by weight TS-1; (b) 1.2% in
    20 weight TS-1; (e) 2.3% by weight TS-1; (d) 4.6% by weight TS-1; (e) 9.2% by weight TS-1). Reaction conditions: 4.6% in furfural weight, 323 K, molar ratio H20 2 / F = 7.5 (.) Furfural conversion; (e) AM performance; (...) AMa performance; (.) AS performance; ("') AF yield; (6.) AFum yield; (O) AFur yield; (O) 5-hydroxyfuranone yield; ( 7) 5-furan yield.
    25 Figure 5: Effect of furfural concentration. Reaction conditions: mass ratio TS-1 / F = 1; 323 K, molar ratio H20 2 / F = 7.5 (.) Furfural conversion; (.) AM performance; ("') AMa yield; (....) AF yield; (O) 5-hydroxyfuranone yield).
    Figure 6: Catalyst reuse for 4.6% in furfural weight, 323 K, molar ratio H20 2 / F = 7.5; 4.6% by weight TS-1, 7 h reaction. Before testing the TS-1 in a new reaction, the catalyst was centrifuged, washed with distilled water and dried at 333 K overnight. In the reaction named White, no catalyst is used.

    Figure 7: Two-stage process for the oxidation of furfural with TS-1 and Amberlyst 70. Reaction conditions: 4.6% by weight of fuñural, 323 K and 4.6% by weight of each of the catalysts. Symbols: furfural conversion (.); yield 5-hydroxy-furan-2 (5H) one (O); AM (e) yield; AF (T) performance; AMa performance (....); and conversion H20 2
    (O)
    DETAILED DESCRIPTION AND MODE OF EMBODIMENT OF THE INVENTION
    In the present invention the titanium silicate catalyst 1 (T8-1) is used for the reactionof liquid phase oxidation of furfural to AM with hydrogen peroxide as agentoxidizing The procedure comprises the following stages:
    a1) contact the fresh TS-1 catalyst with the reagents necessary to carrycarry out the catalyzed reaction,b1) isolate the catalyst from the reaction medium,a2) reuse the heterogeneous catalyst by contacting the isolated TS-1 in the stageb1) or b2) with the reagents necessary to carry out the catalyzed reaction,b2) isolate the catalyst from the reaction medium,This procedure is characterized in that steps a2) and b2) are performed at least 1time. Preferably, steps a2) and b2) of the process of the present invention areThey perform between 1 and 6 times.
    The reactor used is a round bottom glass batch reactor equipped withthree mouths, one for the addition of reagents, another for the sampling and a third forcontrol the temperature by means of a thermocouple. The sampling consists of aseptum through which a needle is introduced in contact with the reaction mixture. Themagnetic stirring available to the reactor remained constant at 800 rpm. Hereactor is submerged in a thermostated oil bath with which it is possible to regulatethe desired temperature
    First the catalyst is added to the reactor along with the H20 2 and part of the water that isUse as a solvent to complete the total reaction volume. On the other hand itpreheat separately the furfural and the remaining water (used to wash thevessel in which the furfural is heated and then added to the reaction medium), tothat when mixed together with the catalyst and the oxidant, there will be no decrease intemperature too high in the reaction mixture. When the temperature of the

    Mixing the H20 2 and the catalyst reaches the desired value, the remaining reagents are introduced and it is taken as zero time when the desired temperature is reached again. The total volume of reaction mixture is 45 mL.
    Different aliquots (-0.5 mL) were taken at different reaction times for later analysis by HPLC liquid chromatography, using oxalic acid as internal standard. To this end, -0.5 mL of a 0.3 M oxalic solution is added and the resulting sample is diluted by adding between 7 and 10 g of water. The previously filtered sample, with a 0.2 micron nylon syringe filter, is added to a vial for further HPLC analysis.
    In addition to the TS-1 catalyst, acid catalysts, such as Amberlyst-70, have been tested under the same reaction conditions. [http://www.dow.com/products/producUamberlyst70!] and polystyrenesulfonic acid (PSSA). They have been performed in all kinetic cases for 24 hours for the following reaction conditions: 50 ° C, 2.3% by weight of catalyst, 4.6% by weight of furfural and with a molar ratio between oxidizing agent and furfural of fifteen.
    To appreciate the effect of the catalyst, a reaction without a catalyst has also been carried out, only with furfural and with oxidizing agent, which has been called White. Table 1 shows the comparative data for the aforementioned reactions after 7.5 hours of reaction. In all cases a total conversion of furfural is achieved at the time taken as a reference.
    In the scheme of Figure 1 it is shown that in a first reaction stage with acid catalysis the furfural is oxidized to 2-hydroxyfuran lying formic in a BaeyerVilliger reaction. In this way one mole of formic acid is formed for every mole of product detected derived from 2-hydroxyfuran, which is in equilibrium with 2 (5H) -furanone or with 2 (3H) -furanone. The yield to formic acid included in the table does not take into account what has occurred as a result of this first stage, so it probably comes from the over oxidation of furfural or some of the reaction products by action of H20 2.
    Table 1. Comparison of the catalytic properties of TS-1 with acid catalysts in the oxidation of furfural with H20 2. Reaction conditions: 4.6% by weight of furfural; 2.3% by weight catalyst; molar ratio H20 2 / F = 15; 323 K; 7.5 h reaction; total furfural conversion. In the White reaction no catalyst was used.
    P201 431169 07-31-201 4
    Catalyst
    Performance ('lo)
    Amberlyst-70 PSSA TS-l White
    Ac. Maleic (AM) 22.630.743.814, 5
    Ac. (ACE) Succinic25.120.79.8
    Ac. Forum (AF) 1.32.65.96.5
    S-hydroxy-2 (SH) -furanone (5hydrox.) 6.91.6
    2 (SH) -Furanone (S-furan.) 17.211.78.8
    Ac. (AFum) Fumaric4.72.81.8
    Ac. Málico (AMa) 4.46.24.66.6
    Ac. Furoic (AFur) 1.41.2
    The data in the table shows that among all the catalysts that have been tested, the TS-1 catalyst has a higher yield towards AM, so it is more selective towards the product of interest and also decreases the number of products detected. The
    The reaction carried out in a homogeneous phase with the PSSA catalyst has a higher yield at AM than that in which Amberlyst-70 is used. In these last two cases the yield towards AS is quite important, and in fact it is the majority product when Amberlyst-70 is used as a catalyst. Another product that is obtained in significant quantities is 5-furan.
    10 Next, we studied how the reaction variables influence the activity of the catalyst for the production of AM, to establish the optimal operating conditions.
    Effect of reaction temperature
    15 The effect of temperature on the catalytic activity of TS-1 in the oxidation reaction of furfural to AM in the presence of H20 2 for 50oe, 600 and 700 was studied and following the same methodology described above for 4.6% by weight of furfural, 2.3% in

    weight of TS-1 and a molar ratio between H20 2 and furfural of 7.5. Figure 2 shows the kinetics corresponding to the three temperatures studied.
    It can be seen that the temperature accelerates the speed of the reaction, so that the total furfural conversion is achieved for shorter reaction times as the temperature increases. Similarly, the rate of AM formation increases and for short reaction times the yield towards AM obtained is slightly higher as the reaction temperature increases. However, after 24 hours of reaction the amount of AM detected decreases with increasing reaction temperature, so that the total oxidation of the AM formed up to CO2 is probably occurring, since an increase in the amount of AF is not detected in the middle.
    Since the fact of increasing the reaction temperature translates into a slight increase in the yield towards AM, it can be said that a temperature of 50 ° C is sufficient to carry out the oxidation of furfural towards AM with acceptable yields after 7, 5 hours of reaction.
    From the evolution of the concentration of the products as the reaction progresses it can be deduced that in the first place 5-hydroxyfuranone is formed and from the oxidation of the latter, AM is finally formed. In the previous figure it can be seen that the transformation rate of 5-hydroxyfuranone to AM increases as the reaction temperature increases. The other product detected is AMa, which comes from the oxidation of AM.
    Effect of the H20 2 / furfural molar ratio
    The effect of the amount of oxidant in the reaction medium was studied for different H20 2 / Furfural molar ratios, all of them higher than the stoichiometric ratio, keeping the furfural concentration constant at 4.6% by weight. Kinetics were performed for 24 hours at 323 K Y with 2.3% by weight of TS-1, the data of which is shown in Figure 3.
    It can be deduced that a higher concentration of oxidizing agent in the reaction medium results in a higher reaction rate, so that the total furfural conversion is achieved at shorter times. Similarly, an increase in the H20 2 / Furfural molar ratio from 4 to 7.5 translates into a noticeable increase in performance towards AM.

    However, when the amount of oxidizing agent increases to a molar ratio
    of 15 observes a slight increase in yield towards AM at short reaction times, but after 24 hours the yield at AM decreases. Since there is no increase in the amount of AF detected, probably the excess of H20 2 causes a total oxidation of AM to CO ...
    Effect of the TS-lIfurfural mass relationship
    The influence of the amount of catalyst in the oxidation of furfural towards AM was studied for different concentrations of TS-1. In addition, a kinetics without catalyst was performed, to take into account the results of the autocatalytic reaction. The results are shown in Figure 4. In these reactions 4.6% by weight of furfural has been used a molar ratio H20 2 / F of 7.5 and a temperature of 323 K.
    It can be seen that when no catalyst is used (graph (a), the furfural conversion rate for a molar ratio of H20 2 / Furfural of 7.5 is very slow and the main products detected are AS and 5-furan ., obtaining for these compounds yields greater than 30% after 24 hours of reaction A 15% yield towards AM is also detected By adding a small amount of catalyst, which corresponds to a mass ratio TS-1 / F of 0 , 26 (graph (b)], it is observed that the distribution of products changes completely.In this case, the main products are AM and 5-hydroxyfuranone, the presence of 5-furan is not detected, and the yield towards AS decreases importantly, by incorporating a greater amount of TS-1 into the reaction medium to a mass ratio of 0.5 and 1 with respect to the furfural [graphs (c) and (d), respectively], the formation of AS is not detected and it improves both the initial performance to 5-hid roxifuranone as the yield to AM throughout the entire reaction, reaching about 80% yield at AM after 24 hours of reaction when the TS-1 / Furfural mass ratio used is 1. In addition there is an increase in the furfural conversion speed. However, when the amount of TS-1 is increased to a mass ratio of 2 with respect to furfural, it is observed that it hardly has an influence on the yield towards 5-hydroxyfuranone, but nevertheless, a decrease of the yield towards AM is observed, of way that it is not possible to overcome 40% of yield. In this case, there is also an increase in the yield to AF compared to the rest of the reactions studied, so it may be that in this case the fact that there is a greater amount of TS-1 in the reaction medium causes that produce

    Oxidation to AF and finally to CO2 instead of selective oxidation to AM.
    Effect of furfural concentration
    Four reactions were also carried out in which the furfural concentration was modified between 2% and 9.2%, keeping the TS-1 / furfural mass ratio constant at 1 and the H20 2 / furfural molar ratio at 7, 5. These reactions were measured at 323 K for 24 hours.
    10 The results of catalytic activity reflect (see Figure 5) how an increase in the concentration of furfural in the reaction medium causes an increase in the reaction rate. This increase in the rate of AM formation is especially evident when the concentration of funural is increased from 2% to 4.6% by weight. Increasing the concentration of furfural to 7.5% by weight increases the speed of the reaction, so that a yield at AM close to 70% is achieved after 7.5 h of reaction, although after 24 h no It is possible to exceed 80% achieved with a furfural concentration of 4.6% by weight. When the concentration of furfural in the reaction medium is 9.2% by weight, the rate of AM formation is not increased with
    20 with respect to using 7.5% by weight, and the AM yield remains constant for reaction times greater than 6 hours.
    TS-1 catalyst reuse:
    25 The reuse of a catalyst is always interesting, because this reduces operating costs. For this reason, in addition to the measures of catalytic activity and selectivity towards AM, special attention has also been given to the reuse of the TS-1 catalyst after several reaction cycles, testing its resistance against deactivation. The catalytic activity during the cycles of
    The reuse has been measured for a furfural concentration of 4.6% by weight, a H20 2 / furfural molar ratio of 7.5 and 323 K. The TS-1 / furfural mass ratio has also been kept constant, assuming that Catalyst losses do not occur during the reuse operation. The time of each of the reuse reactions is 7.5 hours.

    Figure 6 includes the results obtained from each of the 6 reaction cycles at
    those that the catalyst has been subjected to under the aforementioned conditions, including only the yield to AM, 5-hydroxyfuranone and AF. In addition, the presence of AMa was detected, with a yield of around 3%, which is not shown in the figure. These reactions are performed as follows:
    First, the TS-1 catalyst is contacted with the remaining reagents according to the
    step a1) mentioned above. After 7.5 hours, the catalyst is isolated from the reaction medium according to step b1). This separation is effected by centrifugation. The catalyst is then washed by several cycles of water addition and centrifugation, to wash it of the possible remains of products that have remained on its surface.
    Once washed, it is dried at 60 ° C overnight. The reagents are then reintroduced, according to step a2). After 7.5 hours of reaction, the catalyst is separated again from the medium by centrifugation following step b2), washed with water, dried at 60 ° C and the remaining reagents are introduced again. And so on to perform the different reuse cycles
    Figure 6 shows that the catalyst does not show a significant loss of activity during the 6 measured reaction cycles, so it can be concluded that the catalyst TS1 is reusable in the oxidation reaction of furfural towards AM with hydrogen peroxide under the conditions studied.
    Improvement in the selective use of H20 2 to produce AM with a more efficient use of H202: two-stage process.
    The stoichiometric molar ratio required to oxidize furfural to AM is 3. The maximum yield for MA was achieved by using a molar ratio of 7.5, this is more than double the stoichiometric ratio. The non-selective use of H20 z comes from thermal and catalytic decomposition. When TS-1 is used as a catalyst, the kinetic data shows that, for short reaction times, the oxidation of furfural to 5-hydroxyfuranone is very fast and selective and also occurs with a relatively selective use of H 2Ü 2. Therefore, a a good strategy would be to perform oxidation in two stages; In the first step, oxidize the furfural to 5-hydroxyfuranone using TS-y using an H20 2 / furfural molar ratio close to the stoichiometric one. And in one stage

    subsequently oxidize 5-hydroxyfuranone to AM but using another catalyst other than TS-1, since it decomposes non-selectively to H20 2. Acid catalysts based on sulfonic groups have shown the ability to convert 5-hydroxyfuranone to AM.
    ["Poly- (styrene sulphonic acid): An acid catalyst from polysfyrenewasfe for reactions of interest in biomass valorization", N. Alonso-Fagúndez et al. Catalysis Today 234 (2014) 285
    294].
    In practice, the procedure was as follows: first the oxidation of furfural to 5-hydroxyfuranone was carried out for 4 h, using a H..O .. / furfural molar ratio of 2.4 (slightly above the stoichiometric) and TS-1 as catalyst. Then, the catalyst TS-1 catalyst was filtered off and the second oxidation step was carried out using an Amberlyst 70 sulfonic resin as catalyst. An additional amount of H20 .. was incorporated as to obtain an H20 2 / furfural molar ratio of 2 with respect to the initial furfural concentration. One mole of H ..O .. is needed for the stoichiometric oxidation of 5-hydroxyfuranone to maleic acid, so a slight excess of H..O .. with respect to the stoichiometric is actually being incorporated; but globally it has gone from using 7.5 times to using 4.4 times the stoichiometric amount, that is, with this two-stage procedure less than half hydrogen peroxide is used than the one used in the single-stage procedure with TS-1. Figure 7 shows the results obtained, the yields to the products are referred to the furfural initially loaded.
    After 4 h, oxidation of furfural with TS-1 results in a 70% yield to hydroxyfuranone, the yield of maleic acid was less than 10%. Once the TS-1 catalyst is filtered off and the Amberlyst 70 is incorporated as catalyst and more H..O .., the selective oxidation of 5-hydroxyfuranone to AM occurs progressively. After 24 h of reaction with Amberlyst (equivalent to 28 h of total reaction time) the AM yield is about 76%, very close to that obtained after 24 h with TS-1 (78%). The yield to AM reaches almost 90% after 2 days with Amberlyst.
    Therefore, these results demonstrate that through a two-stage process, using TS-1 first and then Amberlyst 70, furfural can be oxidized to AM with a
    yield at more than 80% And making more efficient use of H .. 02 since an amount very close to the stoichiometric is used.
    权利要求:
    Claims (12)
    [1]
    1.-Procedure for the oxidation of furfural to maleic acid with an oxidizing agent, characterized in that it is carried out with at least titanium silicalite as a catalyst.
    [2]
    2. Process according to claim 1, characterized in that the oxidizing agent is hydrogen peroxide.
    [3]
    3. Method according to any one of claims 1 or 2, characterized in that the molar ratio between the oxidizing agent and the furfural is between 4 and 15.
    [4]
    4. Method according to any one of claims 1 to 3, characterized in that the initial concentration of furfural in the reaction medium is between 2 and 10% by weight.
    [5]
    5. Method according to any one of claims 1 to 4, characterized in that the reaction temperature is between 50 and 70 ° C.
    [6]
    6. Process according to any one of claims 1 to 5, characterized in that titanium silicalite is used as the sole catalyst.
    [7]
    7. Method according to any one of claims 1 to 6, characterized in that the mass ratio between the furfural and the titanium silicalite is between 0.5 and 4.
    [8]
    8. Method according to any one of claims 1 to 5, characterized in that at least a second catalyst is used in addition to the titanium silicalite.
    [9]
    9. Method according to any one of claims 1 to 7, characterized in that it comprises the following steps: - contacting the reaction medium comprising furfural and the oxidizing agent with the titanium silicalite catalyst for a period of time between 1 and 24 hours - isolate the catalyst from the reaction medium by centrifugation or filtration

    [10]
    10. Method according to claim 9, characterized in that the isolated catalyst is reused at least once by contacting it with the reaction medium comprising furfural and the oxidizing agent and then isolating it from the reaction medium.
    11. Method according to claim 10, characterized in that the catalyst isreuse and insulate between 1 and 6 times.
    [12]
    12. Method according to claim 8, characterized in that it comprises the following steps:
    10 - contacting the reaction medium comprising furfural and the oxidizing agent in a molar ratio between 2 and 3 with the titanium silicalite catalyst for a period of time between 2 and 10 hours to obtain 5-hydroxyfuranone-isolate the titanium silicalite catalyst of the reaction medium by centrifugation or filtration
    15 - contacting 5-hydroxyfuranone with the oxidizing agent in an initial oxidizing / furfural agent molar ratio between 1 and 3 in the presence of an acid catalyst with sulfonic groups for a period of time between 24 and 48 hours to obtain acid maleic
    13. Method according to claim 12, characterized in that the oxidizing agent is hydrogen peroxide.
    [14]
    14. Method according to any one of claims 12 or 13, characterized in that:
    25 -the step of obtaining 5-hydroxyfuranone is carried out with a stoichiometric ratio between hydrogen peroxide and furfural of 2.4 and over a period of 4 hours -the isolation of the titanium silicalite catalyst is carried out by filtration. -The acid catalyst with sulfonic groups is Amberlyst 70
    30-The step of obtaining maleic acid is carried out with a molar ratio between hydrogen peroxide and equivalent initial furfural of 2 for a period of 24 hours.
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    同族专利:
    公开号 | 公开日
    ES2558261B1|2016-11-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2018171251A1|2017-03-20|2018-09-27|江南大学|Solid-supported metalloporphyrin catalyst and application thereof in preparation of maleic acid|
    WO2020256556A1|2019-06-21|2020-12-24|Stichting Wageningen Research|Method for preparing maleic acid|
    CN109395760B|2018-11-16|2020-06-09|合肥能源研究院|Catalyst for preparing maleic acid by catalytic oxidation of furfural and preparation method and application thereof|
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