PROCESS FOR PREPARATION OF FURAN-2,5-DICARBOXYLIC ACID AND USE OF A CATALYST

专利摘要:
process for preparing furan-2,5-dicarboxylic acid and using a catalyst. the present invention relates to a process for the preparation of furan-2,5-dicarboxylic acid, which comprises the following steps: the preparation or supply of a starting mixture comprising 5-(hydroxymethyl)furfural (hmf), 5 ,5'-[oxy-bis(methylene)]bis-2-furfural (di-hmf) and water, subjecting said starting mixture to oxidizing conditions in the presence of an oxygen-containing gas and a catalytically effective amount from a heterogeneous catalyst comprising one or more noble metals on a support such that both hmf and di-hmf react to provide furan-2,5-dicarboxylic acid in a product mixture which also comprises water and oxidation by-products . Furthermore, the present invention relates to the use of a catalyst comprising one or more noble metals on a support as a heterogeneous oxidation catalyst to catalyze the reaction of hmf and di-hmf to furan acid in an aqueous starting mixture. -2,5-dicarboxylic acid.
公开号:BR112018000606B1
申请号:R112018000606-8
申请日:2016-07-01
公开日:2022-01-18
发明作者:Alvaro GORDILLO；Holger Werhan；Richard Dehn；Benoit Blank；Joaquim Henrique Teles；Stephan A. Schunk；Markus Piepenbrink；René Backes；Lei Zhang
申请人:Basf Se；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to a process for the preparation of furan-2,5-dicarboxylic acid (FDCA) (compound of Formula (I)) and a corresponding use of a catalyst.
BACKGROUND OF THE INVENTION
[002] Other aspects of the present invention and its preferred embodiments are evident from the following description, the working examples and the appended claims.
[003] FDCA is an important compound for the production of several products, for example, polymers and resins.
[004] With the increasing depletion of fossil raw materials, starting materials based on renewable resources are needed, for example, as alternatives to terephthalic acid (a compound used in the production of polyethylene terephthalate, PET). PET is based on ethylene and p-xylene which, in general, are obtained from oil, natural gas or coal, that is, from fossil fuels. As long as biobased routes to ethylene (eg dehydration of bioethanol) are operated on a commercial scale, direct access to bioterephthalic acid remains difficult. FDCA is the best bi-based alternative to terephthalic acid (for more information, see: Lichtenthaler, FW, "Carbohydrates as Organic Raw Materials" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010) .
[005] FDCA can be copolymerized with monoethylene glycol to provide polyethylene furanoate (PEF), a polyester with properties similar to PET.

[006]FDCA is generally obtained from fructose and/or other hexoses by means of a catalyzed, preferably acid-catalyzed, dehydration to the main intermediate of 5-(hydroxymethyl)furfural (HMF) followed by oxidation in FDCA.

[007] In the dehydration step, by-products are formed, depending on the specific process design. A typical by-product is 5,5'-[oxy-bis(methylene)]bis-2-furfural (di-HMF) (V, see below).
[008] In a typical FDCA preparation process, a starting mixture is prepared that comprises 5-(hydroxymethyl)furfural (HMF) by subjecting a mixture of material, which comprises one, two or more compounds selected from the group that consists of hexoses (monomeric hexose molecules, e.g. fructose), oligosaccharides comprising the hexose units and polysaccharides comprising the hexose units, at reaction conditions such that a mixture comprising the HMF, water and by-products ( e.g. di-HMF) will work. Under the reaction conditions, the oligo- and/or polysaccharides, in general, are depolymerized, and subsequently the resulting monosaccharides, for example, the monomeric hexose molecules, are converted to HMF. Hexoses, oligosaccharides and polysaccharides are usually selected from the group consisting of fructose, glucose and cellulose.
[009] During depolymerization, oligo- or polysaccharides, in general, are converted into monomeric hexose molecules through the hydrolytic cleavage of the ether bonds that connect the different hexose units in an oligo- or polysaccharide molecule (e.g., the cellulose). The products of a typical depolymerization process (monomeric hexose molecules) are present in their aldehyde form.
[010] Normally, according to routines, at least in part, not previously described, depolymerization is conducted using a catalyst, preferably in a one-step procedure. Typically, a hydrophilic solvent (in particular water) is used, for example, to increase the amount of dissolved cellulose, therefore increasing the yield by carrying out the process. It is usually advantageous to drive the conversion of cellulose to HMF through a heterogeneous catalyst to facilitate post-synthetic processing. In a typical depolymerization process, an aqueous solution is used as a solvent which sometimes comprises 50% by weight of water or more, based on the total weight of the depolymerization mixture used.
[011] Alternatively, if monosaccharides are used as a starting material for the preparation of a starting mixture comprising HMF, water and by-products, for example di-HMF, no depolymerization step is necessary.
[012] The monosaccharides produced or supplied are normally subjected to a dehydration process, in which the aldehyde form of monomeric hexose molecules is normally transferred through isomerization (through, for example, ketone-ketone tautomerization) in their ketone form which is later converted to its ring form. After ring closure, the ring-closed hexose molecules formed are normally dehydrated (and optionally further isomerized) resulting in a mixture comprising the HMF, by-products (e.g. di-HMF) and water, which can be used as a basic mixture in a process for the preparation of FDCA (preferably in a purified form).
[013] Due to the insolubility of specific monomeric hexose molecules (for example, fructose) in common organic solvents, the dehydration process step is usually carried out in an aqueous environment, so that an aqueous solution comprising HMF, by-products (eg di-HMF) and water is obtained as a (crude) mixture.
[014] Isolation of HMF from such mixtures is challenging, as HMF is often subjected to secondary reactions, e.g. (still) etherification to di-HMF. This is generally the case when water is removed during processing (see, for example, US patent 2,994,645). Once two HMF molecules are etherified, the amount of by-products produced correspondingly is high.

[015] Therefore, the (raw) mixture comprising HMF and water in general is contaminated with by-products, in particular di-HMF, to some extent, since the separation of HMF from the by-products, especially from di-HMF, is not possible with justifiable effort.
[016] Common by-products (e.g. the by-products as described above), for example, are fructose in its ring form (RFF) (compound of Formula (III)), partially dehydrated fructose in its ring form (from -RFF) (compound of Formula (IV)) and 5,5'-[oxy-bis(methylene)]bis-2-furfural (di-HMF) (compound of Formula (V)). HMF (compound of Formula (II)) and di-HMF can be obtained in significant amounts from biomass, especially from biomass comprising the hexoses and/or oligo- and/or polysaccharides, as described above.

[017] Different teachings regarding the isolation or preparation of FDCA have been reported in the patent literature.
[018] WO 2008/054804 A2 publication refers to "Hydroxymethyl furfural oxidation methods" (title). It is described that a reaction mixture that has a mild basic pH can be provided by adding sodium carbonate, FDCA salts that have a clearly high solubility in said reaction mixture compared to reaction mixtures that have a pH neutral or acidic (see paragraph [0049]).
[019] Publication WO 2008/054804 A2 further describes that twice higher solubility of FDCA is obtained in an acetic acid/water mixture (40:60 volume ratio) compared to the solubility in pure water (see paragraph [0058]).
[020] Publication WO 2013/033081 A2 describes a "process for the production of succinic acid and 2,5-furan dicarboxylic acid" (title). In Examples 46 and 47, a mixture of HMF and di-HMF (mol ratio of HMF:di-HMF is 1:10) is converted to FDCA at 100°C.
[021] US patent 2008/103,318 describes "methods of oxidation of hydroxymethyl furfural" (title) which comprises the step of "providing a starting material that includes the HMF in a solvent comprising water in the reactor". The starting material is contacted "with the catalyst comprising the Pt on the support material wherein the contact is conducted at a reaction temperature of about 50°C to about 200°C".
[022] Publication WO 2012/017052 A1 describes a "process for the synthesis of 2,5-furandicarboxylic acid" (title).
[023] Hicham Ait Rass et al. describe a "selective aqueous-phase oxidation of 5-hydroxymethyl furfural to 2,5-furandicarboxylic acid with respect to Pt/C catalysts" (see article title in GREEN CHEMISTRY, vol. 15, no. 2013, page 2240).
[024] US patent 2,994,645 describes the "purification of hydroxymethyl furfural" (title). A process is described in which "gases and water by heating under a high vacuum" are initially removed.
[025] The solubility of FDCA in aqueous solutions can be increased through the addition of solubilizers. EP 0,356,703 A2 relates to a process for the oxidation of 5-hydroxymethyl furfural (HMF) and describes that precipitation of reaction products during the oxidation of 5-hydroxymethyl furfural can be avoided, especially at relatively low concentrations. high when a solubilizer that is inert to the reaction participants under the selected reaction conditions is added to the reaction mixture. EP 0,356,703 A2 further describes that suitable solubilizers, for example, are glycol ethers which do not have free OH groups, especially dimethyl glycol ether, glycol diethyl ether and glycol ethyl methyl ether. .
[026] Very often, FDCA precipitation leads to the deactivation of the heterogeneous catalyst. Publication WO 2013/191944 A1 describes that, due to the very low solubility of FDCA in water, the oxidation of HMF must be carried out in very dilute solutions, in order to avoid precipitation of FDCA on the surface of the catalyst, since the process otherwise it may no longer be economically driven (see page 3).
[027]Own observations show that FDCA precipitation on the inner and/or outer surface of the catalyst of a heterogeneous catalyst can lead to contamination and possible deactivation of the heterogeneous catalyst. This involves covering or coating the catalytically active constituents of the heterogeneous catalyst through the precipitated FDCA so that the catalytic constituents do not come into contact with the reactants. The effect of such catalyst contamination is that the catalyst does not exhibit the same initial activity, if appropriate, and must be replaced by the new catalytic material which increases costs. Especially in the case of using expensive catalysts, for example platinum catalysts, this course of action is often uneconomical.
[028] The description mentioned above regarding the depolymerization or dehydration step also applies to (i) a process for the preparation of FDCA and (ii) the use of a catalyst, according to the present invention, as described in detail below . In particular, the dehydration step or the successive steps of depolymerization and dehydration can be used to prepare a starting mixture as used in accordance with the present invention.
[029] Despite considerable efforts produced by the industry, there remains a need to provide an improved process for the preparation of FDCA from a starting mixture comprising HMF, di-HMF and water, which avoids or, at the very least, avoids at the very least, it alleviates the disadvantages of the processes known to date and which can be operated in an economically advantageous manner. The process to be favorably specified must: - enable the reduction of the complexity of the reactor configurations known in the prior art, - enable the use of a catalyst that can be easily separated from the product mixture after the reaction. BRIEF DESCRIPTION OF THE INVENTION
[030] According to the present invention, this object is achieved through a process for the preparation of furan-2,5-dicarboxylic acid, which comprises the following step: (a) the preparation or supply of a starting mixture that comprises: - 5-(hydroxymethyl)furfural (HMF) - 5,5'-[oxy-bis(methylene)]bis-2-furfural (di-HMF) and - water, (b) submission of said starting mixture under oxidizing conditions in the presence of a gas containing oxygen and a catalytically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support such that the HMF and di-HMF react to provide the acid furan-2,5-dicarboxylic acid in a product mixture which also comprises water.
[031] The "heterogeneous catalyst", preferably, is a substance that is not water soluble and/or is present in solid form.
[032]The expression "the HMF and the di-HMF that react to provide furan-2,5-dicarboxylic acid" indicates that under the oxidation conditions of step (b) HMF reacts and di-HMF reacts, and a first portion of the resulting furan-2 5-dicarboxylic acid is a product of HMF and a second portion of the resulting furan-2,5-dicarboxylic acid is a product of di-HMF.
[033] The product mixture may also contain oxidation by-products. A non-limiting selection of oxidation by-products, which can be formed under oxidation conditions in step (b) of the process of the present invention, are 2,5-diformylfuran acid (DFF), 5-hydroxymethylfuran-2-carboxylic acid (HMFCA). ), 5-formylfuran-2-carboxylic acid (FFCA).
[034] An "oxygen-containing gas" is a gas comprising gaseous compounds that have one or more oxygen atoms per molecule. A preferred gaseous compound that has one or more oxygen atoms per molecule is molecular oxygen (O2).
[035] Air is a gas that contains oxygen preferably.
[036] The term "oxidation conditions" indicates the conditions suitable for reacting HMF and di-HMF and providing furan-2,5-dicarboxylic acid in said product mixture which also comprises water.
[037] The gas containing oxygen acts as an oxidizing agent.
[038] Several types of reaction vessels can be used in step (b) to drive the reaction of HMF and di-HMF to furan-2,5-dicarboxylic acid (FDCA). In many cases, an autoclave is used to drive the reaction from HMF and di-HMF to FDCA. In many cases, the reaction of HMF and di-HMF to FDCA is carried out in a continuous reactor or a semi-continuous reactor. In other cases, a plug flow or a fixed bed reactor is used.
[039] As described above, in typical prior art processes, the reaction of two molecules of HMF to a dimer molecule (di-HMF) results in a high content of by-products and, therefore, in a low yield of FDCA. In contrast, the process according to the present invention converts HMF and di-HMF into valuable FDCA and therefore the overall yield of industrially important production of FDCA from hexoses is increased. In contrast to the teaching of publication WO 2013/033081 A2, a heterogeneous catalyst is used in the process of the present invention, therefore allowing simplified processing and other treatments of the product mixture and its ingredients.
[040]Furthermore, HMF and di-HMF are highly water soluble, therefore increasing the maximum achievable initial concentration of HMF and di-HMF and therefore optimizing the space-time-yield of FDCA. Additionally, water is relatively inert under the oxidizing conditions of the present invention, as it cannot be oxidized as easily as other solvents (e.g., acetic acid). Therefore, the gas containing the oxygen used as the oxidizing agent is used more efficiently.
[041] Surprisingly, it was found that the presence of HMF in the starting mixture is favorable when the di-HMF is subjected to oxidation conditions in the presence of an oxygen-containing gas and a catalystically effective amount of a heterogeneous catalyst that comprises one or more noble metals on a support and is therefore converted to FDCA. Without wishing to be bound by any theory, it is currently believed that the conversion of HMF initially present to FDCA proceeds in a shorter period of time compared to the conversion of di-HMF to FDCA. After the conversion of the HMF initially present to FDCA, the pH of the reaction mixture reduces, since the product of the FDCA reaction is a dicarboxylic acid. The increasing concentration of protons in the reaction mixture catalyzes the hydrolytic cleavage of di-HMF into two molecules of HMF, therefore increasing the concentration of HMF. In turn, the HMF formed by the cleavage of di-HMF is subsequently quickly converted to FDCA, further reducing the pH and increasing the rate of the cleavage reaction. This makes it possible to produce FDCA from di-HMF in an economically valuable period of time, without the need for additional agents as used in the prior art, e.g. HBr (see example 46 and 47 in publication WO 2013/ 033081) or similar corrosive agents. Therefore, at the start of the reaction, the concentration of HMF must be high enough to initiate the conversion of di-HMF to FDCA (in contrast to publication WO 2013/033081). The deliberate presence of HMF for accelerating a process for the preparation of FDCA from di-HMF, therefore, is a primary reason for the advantages provided by the present invention.
[042] In accordance with the present invention, the oxidation of HMF and di-HMF to FDCA is conducted in a starting mixture comprising water. Preferably, in the starting mixture of step (a), the total weight amount of di-HMF, preferably resulting from a previous process step (e.g., process step (a2) as described below) and the HMF is higher than the total amount of other organic compounds. The starting mixture used in the process according to the present invention in step (a) may comprise a comparatively high total concentration of reactant compound(s), HMF and di-HMF. This regularly leads to the precipitation of FDCA during the catalytic conversion in step (b) and therefore to the product mixture comprising the FDCA in solid or dissolved form and the heterogeneous catalyst in solid form.
[043] In the process, according to the present invention, in step (b), the heterogeneous catalyst and the FDCA may be present in solid form. However, preferably the heterogeneous catalyst is present in solid form and the FDCA is present in dissolved form. A heterogeneous catalyst used in step (b) may be part of a mixture of two, three or more than three heterogeneous catalysts. Typically, the product mixture formed in step (b) of a process according to the present invention comprises at least water and a heterogeneous catalyst in separate phases, but often comprises as an additional solid phase the FDCA product. The proportion of FDCA dissolved in the aqueous phase is normally low, due to the low solubility product of FDCA in water or aqueous solutions. Preferably, the aqueous phase of the product mixture produced in step (b) of the present invention is a solution saturated with respect to FDCA.
[044] The product mixture obtained in step (b) can optionally be subjected to other treatment conditions resulting in a second mixture of products.
[045] Publication WO 2013/191944 A1 describes that under pressure and at a temperature in the range from 120°C to 240°C, FDCA in solid form is dissolved in a suitable aqueous solvent. At the proper temperature and proper pressure, a superheated aqueous solution may comprise a total proportion of dissolved FDCA in the range from 10 to 20% by weight, based on the total amount of the aqueous solution.
[046] Heating under pressure the product mixture from step (b) or the second product mixture obtained by subjecting the product mixture from step (b) to additional treatment conditions, which both comprise FDCA in solid or dissolved form and the heterogeneous catalyst in solid form regularly dissolves at least part of the FDCA deposited on or within the pore system of the heterogeneous catalyst (eg, the pore system of the support material). Preferably, a further step (additional treatment) comprises heating the heterogeneous catalyst as present at the end of step (b) or as present at the end of an intermediate step following step (b) so that the activity of the heterogeneous catalyst after the heating (ie, its ability to act as a catalyst for the oxidation of HMF to FDCA) is increased compared to the heterogeneous catalyst as present at the end of step (b).
[047] More preferably, the process of the present invention comprises a further step (additional treatment), as described above, which comprises heating the heterogeneous catalyst as present at the end of step (b) or as present at the end of an intermediate step following step (b) so that the activity of the heterogeneous catalyst after heating (i.e. its ability to act as a catalyst for the oxidation of HMF to FDCA) is increased, wherein the activity of the heterogeneous catalyst after heating is increased by at least 5%, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 30%, most preferably by at least 50% compared to the activity of the heterogeneous catalyst as present at the end of step (b).
[048] A preferred process of the present invention is wherein the product mixture resulting in step (b) of the process is subjected to the step of additional separation, purification and/or (re)crystallization to obtain the purified FDCA.
[049] In many cases, preferably, it is a process of the present invention, wherein: - the starting mixture has a molar ratio of HMF to di-HMF in the range from 100 to 0.8, preferably, in the range from 100 to 0.9 - and/or - the total weight of HMF and di-HMF in the starting mixture is in the range from 0.1 to 50% by weight, preferably in the range from from 1 to 30% by weight, more preferably in the range from 1 to 30% by weight, most preferably in the range from 1 to 20% by weight, based on the total weight of the starting mixture.
[050] In many practical situations preference is given to the starting mixture having a molar ratio of HMF to di-HMF in the range from 100 to 20, in many other preferred situations it is the range from 10 to 0 ,9.
[051] In the starting mixture, these ranges of molar proportions of HMF and di-HMF and/or this range of the total weight of HMF and di-HMF are preferred, since these values represent optimal values for the production of FDCA from HMF or di-HMF. By working within these ranges, a relatively low amount of by-products is produced and the reaction can be conducted in an economically acceptable period of time.
[052] A concentration greater than 50% by weight of HMF and di-HMF, based on the total starting mixture, is in many cases disadvantageous, as the characteristic solubility of the reaction mixture is altered in such a way that the FDCA produced will likely precipitate, therefore complicating post-synthetic processing.
[053] In many cases, preferably, it is a process of the present invention, wherein the total amount of water in the starting mixture is at least 10% by weight, preferably at least 25% by weight, of more preferably at least 50% by weight, based on the total weight of the starting mixture.
[054] When using water as a solvent in a process of the present invention, an environmentally suitable solvent is used. Furthermore, the higher the water content in the starting mixture, the greater amount of HMF and di-HMF can be dissolved and therefore, the greater amount of FDCA can be produced per batch.
[055] Preferably it is a process of the present invention, wherein the pH of the starting mixture is 4.0 or higher, preferably 4.5 or higher, more preferably 5.0 or higher, most preferably , 5.5 or higher, or the pH of the starting mixture is in the range of from 4.0 to 7.0, preferably the pH of the starting mixture is in the range of from 4.5 to 7.0 more preferably, the pH of the starting mixture is in the range of from 5.0 to 7.0, even more preferably, the pH of the starting mixture is in the range of from 5.5 to 7.0.
[056] Preferably, it is to conduct the conversion of HMF to FDCA in a starting mixture that has a pH of 4.0 or higher, since the FDCA produced is very well soluble in such a reaction mixture with a pH of 4. .0 or higher. Starting mixtures with a pH of less than 4.0 are disadvantageous as a low pH in the starting mixture will result in a product mixture with a correspondingly low pH causing unfavorable precipitation of FDCA.
[057] In the process of the present invention, the addition of solubilizers is optional. Preferably, the starting mixture in step (b) does not comprise a solubilizer for the FDCA.
[058] Preferably, in step (b) of the process of the present invention, the pH development in the mixture subjected to oxidizing conditions is not controlled by the addition of alkaline reagents.
[059] A process of the present invention is preferably wherein the total amount of HMF in the starting mixture is in the range from 0.1 to 40% by weight, preferably in the range from 1 to 30% by weight, based on the total weight of the starting mixture.
[060] As mentioned above, FDCA produced from the HMF initially present accelerates the hydrolytic cleavage of di-HMF and therefore accelerates the overall reaction. Therefore, concentrations of HMF in the starting mixture below 0.1 are not advantageous. On the other hand, a concentration greater than 40% by weight of HMF, based on the total amount of the starting mixture, is disadvantageous as the solubility characteristic of the reaction mixture is altered such that FDCA production is likely to precipitate. .
[061] Especially preferably it is a process of the present invention, wherein the total amount of di-HMF in the starting mixture is in the range from 0.1 to 40% by weight, preferably in the range from 0.1 to 40% by weight. from 0.1 to 30% by weight, more preferably in the range from 0.1 to 10% by weight, most preferably in the range from 0.2 to 6% by weight, based on in the total weight of the starting mixture.
[062] A concentration greater than 40% by weight of di-HMF, based on the total weight of the starting mixture, is disadvantageous as the solubility characteristic of the reaction mixture is altered such that FDCA production is likely to precipitate.
[063] Preferably it is a process of the present invention, wherein the pH of the product mixture is less than 7 and wherein, preferably, the pH of the product mixture is in the range from 1 to 4.
[064] In accordance with the present invention, the pH of the reaction mixture can be monitored in order to correspondingly monitor the conversion to FDCA during the reaction process. Preferably, it is to have a product mixture that has a pH of less than 7 (preferably less than 4), which generally means that an economically valuable amount of HMF or di-HMF to FDCA has been converted.
[065] Preferably, it is a process of the present invention, wherein said starting mixture at a temperature in the range from 70°C to 200°C, preferably in the range from 80°C to 180°C more preferably in the range from 90°C to 170°C, most preferably in the range from 100°C to 140°C, is subjected to said oxidation conditions in the presence of said gas containing oxygen and said catalystically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support, such that the HMF and di-HMF react to provide furan-2,5-dicarboxylic acid in the product mixture, which also comprises the by-products of water and oxidation.
[066] On the one hand, lower reaction temperatures typically result in a reduced reaction rate, therefore significantly increasing the time required for the oxidation of HMF or di-HMF to FDCA and making the process economically inefficient.
[067] On the other hand, very high temperatures can lead to overoxidation, a very high reaction rate, an increased production of oxidation by-products and poorly controllable reaction conditions that require costly safety measures.
[068] In many cases, a preferred process is as described above (or as preferably described above), wherein said starting mixture is subjected to said oxidation conditions in a pressurized reactor, wherein during said reaction of HMF and di-HMF, the FDCA oxygen or the gas containing the oxygen is continuously (or optionally and, less preferably, discontinuously) and is simultaneously removed from said reactor
[069] In some cases, the pressure at which the reaction is conducted depends on the headspace volume of the reactor used which needs to accommodate at least the required stoichiometric amount of oxygen-containing gas to completely convert the HMF and di reactants. -HMF. A high pressure (e.g. 20 (2 MPa) or e.g. up to 100 bar (10 MPa)) is required in cases where no continuous or discontinuous supply of a gas containing oxygen is used, e.g. in a case where the reactor is pressurized once with at least a stoichiometric amount of an oxygen-containing gas at the start of the reaction without any further manipulation of the pressure in the reactor.
[070] In other cases, the gas containing the consumed oxygen is continuously or discontinuously replaced by the gas containing the fresh oxygen. In such cases, preferably, it is a partial pressure of oxygen in the range from 200 mbar (0.02 MPa) and 10 bar (1 MPa).
[071] A process of the present invention is preferably wherein said starting mixture is subjected to said oxidation conditions in a pressurized reactor, wherein the partial pressure of oxygen in the reactor is at least temporarily in the range from 100 mbar (0.01 MPa) to 20 bar (2 MPa), preferably in the range from 200 mbar (0.02 MPa) to 10 bar (1 MPa), during the reaction of HMF and di-HMF for furan-2,5-dicarboxylic acid.
[072] A person skilled in the art will select the appropriate oxidation conditions according to your specific needs. In many cases, the oxidation is carried out at a pressure of 1 to 100 bar, preferably at a pressure of 1 to 20 bar (0.01 to 2 MPa) in an atmosphere of a gas containing oxygen or a mixture of oxygen. a gas that contains the oxygen and another gas (which is preferably inert under the reaction conditions).
[073] Working under a pressure greater than 1 bar (0.01 MPa) is not preferred as it requires additional technical measures, therefore increasing the complexity of the reaction system. To work with pressures greater than 20 bar (2 MPa), additional safety equipment is required to meet specific safety requirements.
[074] A preferred process of the present invention is wherein said starting mixture does not comprise a catalystically effective amount of a homogeneous oxidation catalyst selected from the group of cobalt, manganese and bromide compounds and mixtures thereof.
[075] To separate a homogeneous oxidation catalyst from a reaction mixture, technically complicated separation units are required in the overall product installation, increasing material and energy costs. Therefore, in accordance with the present invention, the presence of one or more homogeneous oxidation catalysts is preferably not.
[076] More specifically, preferably, it is a process of the present invention wherein the total amount of cobalt and manganese and bromide ions in the starting mixture is less than 100 ppm, preferably less than 20 ppm.
[077] It is of special interest to avoid toxic or corrosive compounds, in particular, cobalt and manganese compounds, as well as bromide compounds. The latter drastically increases the corrosivity of the reaction mixture and therefore requires specially coated reactor vessels which incur high costs.
[078] A process of the present invention preferably is wherein the total amount of carboxylic acid and carboxylic acid ions in the starting mixture is less than 10% by weight, preferably less than 5% by weight.
[079] Depending on the nature of the acid, for example the number of acid groups per molecule and its specific structure, the presence of a specific carboxylic acid or its anions modifies the pH of the reaction mixture and therefore complicates monitoring. of the progress of FDCA formation reactions by pH. This effect is even more pronounced as the carboxylic acids present can be oxidized by an oxygen-containing gas under the oxidation conditions of step (b) as described above for compounds with a change in acidity, which can affect even more the pH. In this case, pH could no longer be used as a measure for the progress of FDCA formation reactions.
[080] In addition, secondary reactions between carboxylic acids and oxygen-containing gases result in an inefficient use of the oxygen-containing gas as an oxidizing agent for HMF and di-HMF.
[081] A process of the present invention is preferably wherein the total amount of acetate and acetic acid ions in said starting mixture is less than 10% by weight, preferably less than 1% by weight.
[082] A process of the present invention is preferably, wherein the step of preparing said starting mixture (according to step (a)) comprises: - (a1) preparing or supplying a mixture of material comprising : - one, two or more compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units and polysaccharides comprising hexose units, - a2) subjecting said mixture of material to the reaction conditions in a manner that a resulting mixture comprises: - the HMF - the di-HMF and - the water, (a3) optionally subjecting the mixture resulting from step (a2) to additional treatment conditions, preferably without the addition of a carboxylic acid and/or without the addition of an acidic solvent to dissolve the HMF and di-HMF, - so that said starting mixture results.
[083] The term "acidic solvent" indicates a mixture of aqueous solvent that has a pH of less than 6 and/or a solvent (aqueous or non-aqueous) that comprises a substance that has a pKa of less than 5.
[084]The process step of subjecting the mixture to reaction conditions such that a mixture comprising the HMF, di-HMF and water (i.e. process step (a2) as defined above) often comprises a depolymerization and/or dehydration process as described above. All aspects of a depolymerization and/or dehydration step discussed herein in the context of a process for preparing a starting mixture for a process for preparing furan-2,5-dicarboxylic acid apply mutatis mutandis to a process , in accordance with the present invention.
[085] In some cases, it is advantageous to carry out the depolymerization and dehydration step (step (a2) as defined above) using the same catalyst and/or the same reaction mixture and/or the same reactor.
[086] In particular, preferably, it is a step of preparing said starting mixture as described above (or preferably described above) in which process step (a3) is omitted (no additional treatment conditions are necessary, for (e.g. solvent change) and the resulting mixture in process step (a2) is the starting mixture prepared in process step (a) and subjected to oxidation conditions in process step (b).
[087] In some cases, it is advantageous to carry out the depolymerization and dehydration step (step (a2)) and the oxidation of HMF and di-HMF to FDCA (step (b)) in the same reactor.
[088] As described above, di-HMF is produced as a by-product during the conversion of hexoses or oligosaccharides or polysaccharides (eg cellulose) to HMF. Therefore, it is a further embodiment of the present invention that di-HMF and HMF are converted to FDCA and therefore contribute to an increase in the overall yield of the process. The addition of acid solvent and/or carboxylic acid should be avoided to enable monitoring of the reaction process by measuring the pH.
[089] Another advantage of the process of the present invention, as described above, is the use of water as a solvent. According to the present invention, preferably, after successful conversion of said two or more compounds selected from the group consisting of hexoses, oligosaccharides comprising the hexose units and polysaccharides comprising the hexose units in HMF (and di-HMF), the mixture of aqueous material obtained in step (a2) (or the mixture of aqueous material obtained after further treatment in step (a3)) is directly fed into the reactor, where the produced HMF and di-HMF are converted to FDCA (according to step (b) of the present invention).
[090] However, it is even more advantageous if the process steps (a2) and (b) are carried out in the same reactor, with an intermediate step (a3) in the same reactor or without an intermediate step (a3). Thereby, the need for complicated and expensive solvent separation, solvent exchange or solvent purification between steps (a2) and (b) is reduced or avoided. In many cases, two heterogeneous catalysts are used in step (a2) and in step (b). However, in some cases, the catalyst may be the same for both steps. Therefore, the overall process can be simplified using the same solvent system throughout steps (a1) to (b).
[091] In particular, preferably, it is a process of the present invention, wherein, in said heterogeneous catalyst comprising one or more noble metals on a support (i) at least one of said noble metals is selected from the group consisting of gold, platinum, iridium, palladium, osmium, silver, rhodium and ruthenium, - and/or (ii) said support is selected from the group consisting of carbon, metal oxides, metal halides and metal carbides .
[092] The specific noble metals, as indicated above in item (i), catalyze the reaction of HMF in FDCA. Suitable supports for immobilizing the noble metals, as mentioned above, are the supports mentioned above in item (ii) as they do not adversely affect the reaction kinetics during the conversion of di-HMF and HMF to FDCA.
[093] A process of the present invention is especially preferably, wherein in said heterogeneous catalyst comprising one or more noble metals on a support - at least one of said noble metals is selected from the group consisting of platinum, iridium, palladium, osmium, rhodium and ruthenium, preferably platinum, - and - said the support is carbon.
[094] Carbon is a suitable support to immobilize noble metals as described above, especially platinum, since it does not negatively influence the reaction kinetics of HMF and di-HMF conversion to FDCA.
[095] A process of the present invention is preferably wherein, in said heterogeneous catalyst, it comprises one or more noble metals on a support - said one or one of said more noble metals is platinum and that support is carbon, - and - the platinum content in the support is in the range from 0.1 to 20% by weight, preferably from 1 to 10% by weight, based on the total weight of the heterogeneous catalyst comprising one or more noble metals on a support.
[096] In order to sufficiently accelerate the reaction of HMF and di-HMF in FDCA, the platinum loading on the support should be at least 0.1% by weight (preferably at least 1% by weight) , based on the total weight of heterogeneous catalysts comprising one or more noble metals on a support.
[097] In contrast, therefore, if too much platinum is immobilized on a support, the conversion per atom of platinum reduces due to a lower average accessibility of platinum atoms, therefore, leading to greater waste of noble metals and, therefore higher costs.
[098] A process of the present invention is preferably wherein, in said heterogeneous catalyst comprising one or more noble metals on a support, the molar ratio of said one or more more noble metals to the total amount of HMF and di -HMF is in the range from 1:1,000,000 to 1:10, preferably in the range from 1:10,000 to 1:10, most preferably in the range from 1:1,000 to 1: 100, even more preferably, one or one of said more noble metals is platinum.
[099] It is advantageous to convert as much HMF and di-HMF per noble metal atom as possible to FDCA to increase the FDCA yield per batch and to efficiently utilize the precious noble metal.
[0100] A process of the present invention is preferably, wherein the process is not a process comprising all of the following steps: (A) in an aqueous reactant mixture, catalytically converting one or more organic reactant compounds by means of at least , a heterogeneous catalyst, so as to form a first product suspension comprising furan-2,5-dicarboxylic acid in solid form and the heterogeneous catalyst in solid form (B) heating under pressure (1) this suspension of the first product , or (2) a second product suspension prepared therefrom by post-treatment, each comprising the furan-2,5-dicarboxylic acid in solid form and the heterogeneous catalyst in solid form, such that the furan-2,5-dicarboxylic acid 2,5-dicarboxylic acid dissolves fully or partially, resulting in a first aqueous product phase comprising dissolved furan-2,5-dicarboxylic acid, and then (C) separation of the heterogeneous catalyst from this p first aqueous product phase comprising dissolved furan-2,5-dicarboxylic acid, or from a second product phase resulting therefrom through further treatment and comprising dissolved furan-2,5-dicarboxylic acid.
[0101] A process of the present invention preferably is wherein the product mixture obtained in step (b) comprises FDCA in dissolved form, and wherein the product mixture obtained in step (b) preferably does not comprise the FDCA in solid form.
[0102] As described above, FDCA precipitation in the presence of a heterogeneous catalyst is highly disadvantageous, since the effect of FDCA precipitation is that both the heterogeneous catalyst and the FDCA are present in solid form and can no longer be separated. each other in a simple way. As described above, very often, precipitation of FDCA incidentally leads to deactivation of the heterogeneous catalyst. The precipitation of FDCA on the inner and/or outer surface of the catalyst of a heterogeneous catalyst can lead to contamination and possible deactivation of the heterogeneous catalyst. This involves covering or coating the catalytically active constituents of the heterogeneous catalyst through the precipitated FDCA so that the catalytic constituents do not come into contact with the reactants. The effect of such catalyst contamination is that the catalyst does not exhibit the same initial activity, if appropriate, and must be replaced by the new catalytic material which increases costs. Especially in the case of using expensive catalysts, for example platinum catalysts, this course of action is often uneconomical.
[0103] The present invention also relates to the use of a catalyst comprising one or more noble metals on a support as a heterogeneous oxidation catalyst to accelerate in an aqueous starting mixture for the conversion of HMF and di-HMF to acid furan-2,5-dicarboxylic acid. At present, the catalyst is preferably a catalyst as defined above or in the appended claims. Preferably, it is the use of a catalyst comprising one or more noble metals (preferably gold, platinum, iridium, palladium, osmium, silver, rhodium and ruthenium) on a support (preferably carbon, metal oxides, metal halides and metal carbides). Furthermore, the use of a catalyst comprising one or more noble metals on a support as a heterogeneous oxidation catalyst makes it possible to carry out steps (a1), (a2), optionally (a3) and (b) without exchanging solvents and without the addition of expensive chemicals such as acetic acid.
[0104] In general, all aspects of the present invention discussed above herein in the context of a process for preparing furan-2,5-dicarboxylic acid according to the present invention apply mutatis mutandis to the use of a catalyst , in accordance with the present invention. And similarly, all aspects of the present invention's use of a catalyst discussed herein above or below apply mutatis mutandis to a process for preparing furan-2,5-dicarboxylic acid in accordance with the present invention.
[0105] Preferably, it is the use of a catalyst according to the present invention in processes as described above, especially in FDCA manufacturing processes. All aspects of or associated with the processes of the present invention as described above (or preferably described above) may also be conducted by or in combination with the use of a catalyst in accordance with the present invention.
[0106]By using a catalyst in accordance with the present invention, it is possible to simultaneously convert di-HMF and HMF into valuable FDCA and therefore increase the overall yield of important industrial production of FDCA from hexoses (e.g. , fructose), and the like.
[0107] Other advantages of a use of a catalyst in accordance with the present invention are as described herein above, generally in the context of the process of the present invention and more specifically with respect to the preferred aspects of this process.
[0108] In many cases, preferably, it is the use, in accordance with the present invention, of a catalyst, wherein the pH of the starting mixture is 4.0 or greater, preferably 4.5 or greater, of more preferably, the pH of the starting mixture is in the range of from 4.0 to 7.0, more preferably, the pH of the starting mixture is in the range of from 4.5 to 7.0. The corresponding advantages are as discussed above.
[0109] Accordingly, it is an embodiment of the present invention to enable a use of the catalyst, as defined above, which is active in converting both HMF and di-HMF to FDCA and can be easily separated and later reused.
[0110] The present invention is further described in detail below through specific aspects: (1) A process for the preparation of furan-2,5-dicarboxylic acid which comprises the following step: (a) the preparation or supply of a mixture starting material comprising: - 5-(hydroxymethyl)furfural (HMF) - 5,5'-[oxy-bis(methylene)]bis-2-furfural (di-HMF) and - water, (b) subjecting said starting mixture to oxidizing conditions in the presence of a gas containing oxygen and a catalystically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support so that the HMF and di-HMF react to providing the furan-2,5-dicarboxylic acid in a product mixture which also comprises water. (2) Process according to aspect 1, wherein: - the starting mixture has a molar ratio of HMF to di-HMF in the range from 100 to 0.8, preferably in the range from 100 to 0.8 100 to 0.9, - and/or - the total weight of HMF and di-HMF in the starting mixture is in the range from 0.1 to 50% by weight, preferably in the range from 1 to 30 % by weight, more preferably in the range from 1 to 30% by weight, most preferably in the range from 1 to 10% by weight, based on the total weight of the starting mixture. (3) A process according to any preceding aspect, wherein the total amount of water in the starting mixture is at least 10% by weight, preferably at least 25% by weight, more preferably at least , 50% by weight, based on the total weight of the starting mixture. (4) A process according to any preceding aspect, wherein the pH of the starting mixture is 4.0 or higher, preferably 4.5 or higher, more preferably 5.0 or higher, most preferably , 5.5 or higher, or the pH of the starting mixture is in the range of from 4.0 to 7.0, preferably the pH of the starting mixture is in the range of from 4.5 to 7.0 more preferably, the pH of the starting mixture is in the range of from 5.0 to 7.0, even more preferably, the pH of the starting mixture is in the range of from 5.5 to 7.0. (5) Process according to any preceding aspect, wherein the total amount of HMF in the starting mixture is in the range from 0.1 to 40% by weight, preferably in the range from 1 to 30% by weight, based on the total weight of the starting mixture. (6) A process according to any foregoing aspect, wherein the total amount of di-HMF in the starting mixture is in the range from 0.1 to 40% by weight, preferably in the range from 0. 1 to 30% by weight, more preferably in the range from 0.1 to 10% by weight, even more preferably in the range from 0.2 to 6% by weight, based on the total weight of the starting mix. (7) A process according to any preceding aspect, wherein the pH of the product mixture is less than 7 and wherein, preferably, the pH of the product mixture is in the range from 1 to 4. (8) A process according to any preceding aspect, wherein said starting mixture at a temperature in the range from 70°C to 200°C, preferably in the range from 80°C to 180°C, more preferably , in the range from 90°C to 170°C, even more preferably, in the range from 100°C to 140°C, is subjected to said oxidation conditions in the presence of said oxygen-containing gas and said catalytically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support such that both HMF and di-HMF react to provide furan-2,5-dicarboxylic acid in the product mixture, also comprising water and oxidation by-products. (9) Process according to any preceding aspect, wherein said starting mixture is subjected to said oxidation conditions in a pressurized reactor, wherein during said reaction of HMF and di-HMF the FDCA oxygen or a gas containing oxygen is continuously fed into and simultaneously removed from said reactor. (10) Process according to any preceding aspect, wherein said starting mixture is subjected to said oxidation conditions in a pressurized reactor, wherein the partial pressure of oxygen in the reactor is at least temporarily in the range from 200 mbar to 50 bar (0.02 to 5 MPa), preferably in the range from 1 to 20 bar (1 to 2 MPa), during the reaction of HMF and di-HMF to furan-2 acid, 5-dicarboxylic acid. (11) A process according to any preceding aspect, wherein said starting mixture does not comprise a catalystically effective amount of a homogeneous oxidation catalyst selected from the group of cobalt, manganese and bromide compounds and mixtures thereof. (12) Process according to any preceding aspect, wherein the total amount of cobalt and manganese ions and bromide in the starting mixture is less than 100 ppm, preferably less than 20 ppm. (13) Process according to any foregoing aspect, wherein the total amount of acetate and acetic acid ions in said starting mixture is less than 10% by weight, preferably less than 1% by weight. (14) Process according to any preceding aspect, wherein the total amount of carboxylic acid and carboxylic acid ions in the starting mixture is less than 10% by weight, preferably less than 5% by weight. (15) Process according to any preceding aspect, wherein the step of preparing said starting mixture comprises: (a1) preparing or supplying a mixture of material comprising: - one, two or more compounds selected from from the group consisting of hexoses, oligosaccharides comprising hexose units and polysaccharides comprising hexose units, (a2) subjecting said mixture of material to reaction conditions so that a resulting mixture comprises: - the HMF - di-HMF and - water, (a3) optionally subjecting the mixture resulting from step (a2) to additional treatment conditions, preferably without the addition of a carboxylic acid and/or without the addition of an acid solvent to dissolve the HMF and di-HMF, - so that said starting mixture results. (16) Process according to any preceding aspect, wherein in said heterogeneous catalyst comprising one or more noble metals on a support (i) at least one of said noble metals is selected from the group consisting of gold, platinum, iridium, palladium, osmium, silver, rhodium and ruthenium, - and/or (ii) said support is selected from the group consisting of carbon, metal oxides, metal halides and metal carbides. (17) Process according to any preceding aspect, wherein in said heterogeneous catalyst comprising one or more noble metals on a support - at least one of said noble metals is selected from the group consisting of platinum, iridium, palladium, osmium, rhodium and ruthenium, preferably platinum - and - said the support is carbon. (18) Process according to any preceding aspect, wherein in said heterogeneous catalyst comprising one or more noble metals on a support - said one or one of said more noble metals is platinum and the support is carbon, - and - the platinum content in the support is in the range from 0.1 to 20% by weight, preferably from 1 to 10% by weight, based on the total weight of the heterogeneous catalyst comprising one or more noble metals on a support. (19) A process according to any preceding aspect, wherein in said heterogeneous catalyst comprising one or more noble metals on a support - the molar ratio of said one or one of said more noble metals to the total amount of HMF and di -HMF is in the range from 1:1,000,000 to 1:10, preferably in the range from 1:10,000 to 1:10, most preferably in the range from 1:1,000 to 1:100 preferably one or one of said nobler metals is platinum. (20) A process according to any preceding aspect, wherein the process is not a process comprising all of the following steps: (A) in an aqueous reactant mixture, catalytically converting one or more organic reactant compounds by means of at least , a heterogeneous catalyst, so as to form a first product suspension comprising furan-2,5-dicarboxylic acid in solid form and the heterogeneous catalyst in solid form (B) heating under pressure (1) this suspension of the first product , or (2) a second product suspension prepared therefrom by further treatment, - each comprising furan-2,5-dicarboxylic acid in solid form and the heterogeneous catalyst in solid form, such that the acid furan-2,5-dicarboxylic acid dissolves fully or partially, resulting in a first aqueous product phase comprising dissolved furan-2,5-dicarboxylic acid and then (C) separating the heterogeneous catalyst from this p first aqueous product phase comprising dissolved furan-2,5-dicarboxylic acid, or from a second product phase resulting therefrom through further treatment and comprising dissolved furan-2,5-dicarboxylic acid. (21) A process according to any preceding aspect, wherein the product mixture obtained in step (b) comprises furan-2,5-dicarboxylic acid in dissolved form and wherein the product mixture obtained in step (b) ) preferably does not comprise furan-2,5-dicarboxylic acid in solid form. (22) Use of a catalyst comprising one or more noble metals on a support as a heterogeneous oxidation catalyst to accelerate in an aqueous starting mixture for the conversion of HMF and di-HMF to furan-2,5-dicarboxylic acid , wherein the catalyst is preferably a catalyst as defined in any one of aspects 1 to 21. (23) Use of a catalyst, according to aspect 22, wherein the pH of the starting mixture is 4.0 or higher, preferably 4.5 or higher, more preferably, the pH of the starting mixture is in the range of from 45.0 to 7.0, more preferably, the pH of the starting mixture is in the range of 4 .5 to 7.0.
[0111] Throughout the present text, the preferred aspects and features of the present invention, i.e., the process of the present invention and the use of the present invention, are preferably combined with each other in order to achieve the processes and uses especially preferably in accordance with the present invention.
[0112]The invention is illustrated in detail below by examples. EXAMPLES CATALYST SCREENING EXPERIENCES
[0113]Catalyst scanning was performed in a series of unique experiments labeled "Experiment 1" to "Experience 3". In each single experiment from "1" to "3", the organic reactant compounds HMF and di-HMF, in parts, were catalytically converted by means of a heterogeneous platinum catalyst to the FDCA. The general experimental procedure for each screening experiment from "1" to "3" was as follows: In a first step, by filling in a steel autoclave reactor (internal volume of 90 mL), specific amounts of detured water (D2O , 99.9 carbon atoms, Sigma Aldrich (151882)), HMF (99+%) and di-HMF (99+%) An aqueous mixture of starting material was prepared which has a similar composition to the composition of feed streams. of HMF normally obtained in the dehydration of sugar). The amounts of reagents and D2O are identified in Table 1 below: TABLE 1
*di-HMF, for example, can be synthesized according to WO 2013/033081, Example 45.
[0114]The starting concentration C0[HMF+di-HMF] of HMF + di-HMF in each aqueous reagent mixture was correspondingly 5% by weight, based on the total mass of the aqueous mixture of reagents (total mass of deuterated water , HMF and di-HMF). The solid heterogeneous catalyst (0.928 g of Pt/C at 5% by weight, 50% by weight of H2O) was added to the respective aqueous reagent mixture and therefore a reaction mixture was obtained comprising deuterated water, HMF , di-HMF and the heterogeneous catalyst.
[0115] In a second step, the filled reactor was hermetically sealed and pressurized with synthetic air (total pressure of 100 bar (10 MPa) to obtain the conditions for the HMF and di-HMF to react to provide the FDCA The starting mixture in the reactor comprising the HMF, di-HMF and the deutrated water was heated to a temperature of 100°C while stirring at 2000 rpm. After reaching 100°C, this temperature was maintained for 18 hours while continuing stirring the heated and pressurized reaction mixture during the reaction time. A product mixture comprising the FDCA, oxidation by-products, detured water, and the heterogeneous catalyst resulted.
[0116] In a third step, after the temperature has been maintained for 18 hours, to provide a cooled product mixture, the steel autoclave reactor can: (i) cool down to room temperature (about 22o C), ( ii) be depressurized and (iii) be opened.
[0117]The product mixture obtained was in the form of a suspension.
[0118] For the purpose of analyzing the product of the cooled product mixture, a solution of deuterated sodium hydroxide (NaOD, 40% by weight in D2O, 99.5 atoms of D atom, Sigma Aldrich) was carefully added until the mixture was mixed. of slightly alkaline product reached a pH in the range of 9 to 10. The slightly alkaline product mixture comprised the disodium salt of FDCA in fully dissolved form and the heterogeneous catalyst in solid form.
[0119] In a fourth step, the heterogeneous catalyst in the mixture of slightly alkaline products was separated from the solution through syringe filtration and the filtrate (i.e. the remaining solution comprising the disodium salt of FDCA in completely dissolved form) was subsequently analyzed by 1H NMR spectroscopy. 1H NMR spectroscopy was used to determine the concentration of FDCA, FFCA, HMF and di-HMF. NMR ANALYSIS NMR SAMPLE PREPARATION AND NMR MEASUREMENTS
[0120] 3-(Trimethylsilyl)propionic acid-d4 sodium salt (Standard 1, 68.39 mg, corresponding to 0.397 mmol, 98% in D atom, Alpha Aesar (A14489)) and tetramethylammonium iodide (Me4N + I-, Standard 2, 80.62 mg, corresponding to 0.397 mmol, 99%, Alfa Aesar (A12811)) as internal standards at 5.0 g of a slightly alkaline product mixture, exhibiting a pH value in the range a from 9 to 10. Finally, 0.7 ml of this prepared liquid sample was transferred to an NMR tube for 1H NMR quantitation experiments.
[0121] NMR spectra were recorded in D2O at 299 K using a Bruker-DRX 500 spectrometer with a 5 mm probe of DUL 13-1H / 19F Z-GRD Z564401 / 11, with a measurement frequency of 499.87 MHz The Recorded Data was processed with Topspin 2.1, Patchlevel 6 software (Supplier: Bruker BioSpin GmbH, Silberstreifen 4, 76287 Rheinstetten, Germany). INTERPRETATION OF NMR SPECTRUM
[0122]The interpretation of NMR spectra is based on published reference data as indicated below.
[0123] The disodium salt of FDCA (disodium salt of the compound of Formula (I)): 1H NMR (500 MHz, D 2 O, 299 K): 6.97 ppm (2H, s, furan-H); 13C {1H} NMR: 166.1 ppm (-COO), 150.0 ppm (furan C atoms), 115.8 ppm (furan C atoms).
[0124] Reference: J. Ma, Y. Pang, M. Wang, J. Xu, H. Ma and X. Nie, J. Mater. Chem., 2012, 22, 3457-3461.
[0125] The sodium salt of FFCA (sodium salt of the compound of Formula V): 1H NMR (500 MHz, D 2 O, 299 K): 9.49 ppm (1H, s, -CHO); 7.42 ppm (1H, d, 3J = 3.67 Hz, furan-H); 7.03 ppm (1H, d, 3J = 3.67 Hz, furan-H).
[0126] Reference: A.J. Carpenter, D.J. Chadwick; Tetrahedron 1985, 41 (18), 3803-3812. SCREENING EXPERIENCES
[0127] In each individual experiment, a cooled product mixture was obtained, and based on it, a slightly alkaline product mixture comprising the disodium salt of FDCA in completely dissolved form. As illustrated in Table 1, the conversion of HMF in molar percentage (%) and the yield in molar percentage (%) are summarized. TABLE 1 RELEVANT PARAMETERS OF CATALYST SCREENING EXPERIMENTS
TABLE 2 RELEVANT PARAMETERS OF THE CATALYST SCREENING EXPERIENCES

[0128]The conversion of HMF in molar percentage (%) was calculated as follows (the conversion of di-HMF was calculated accordingly): - Conversion of HMF [% in mol] = [1-(Cfinal [HMF] / C0[HMF]))] * 100, - where C[HMF] is the concentration in percent (%) by weight measured in the slightly alkaline product mixture and C0[HMF] is the concentration in percent (%) by weight measured based on the amount of HMF added and the volume of the starting mixture.
[0129] The "conversion [% in mol]" and the "yield [% in mol]" are average values calculated from a first value based on internal standard 1 and a second value based on internal standard 2 (the overall deviation is less than 5%).
[0130]The definition of yield (exemplified for the FDCA):
- where - n[FDCA] = [FDCA in mol (based on standard 1) + FDCA in mol (based on standard 2)] / 2 - n[HMF] = m0[HMF]/ M[HMF] - n[di-HMF] = m0[di-HMF] / M[di-HMF] - where C[FDCA] is the concentration of FDCA in percent (%) by weight in the filtrate obtained in the fourth step, C0[HMF] is the starting concentration of HMF in percent (%) by weight, CO[di-HMF] is the starting concentration of di-HMF in percent (%) by weight, MFDCA, MHMF and Mdi-HMF are the respective molecular weights in g/mol.
[0131] The yield [% in mol] for the FFCA was determined mutatis mutandis for the yield of FDCA.
[0132]The amount of HMF converted based on the amount of HMF and di-HMF (CHMF + di-HMF) was calculated by the following Formula:

[0133] The minimum yield of di-HMF (Ymin,di-HMF) was calculated by: - Ymin, di-HMF = YFDCA - CHMF+di-HMF
[0134] In Table 1, the results of the three experiments described above are shown. In all three experiments, the molar amount of FDCA obtained after oxidation is greater than the molar amount of HMF provided at the beginning of the corresponding experiment. Therefore, di-HMF was successfully converted to FDCA with considerable yield.
[0135]Furthermore, Table 1 shows that FDCA yield is increasing with increasing nHMF / (nHMF + 2ndi-HMF) ratio.

权利要求:
Claims (17)
[0001]
1. PROCESS FOR THE PREPARATION OF FURAN-2,5-DICARBOXYLIC ACID, characterized in that it comprises the following steps: (a) the preparation or supply of a starting mixture comprising: - 5-(hydroxymethyl)furfural (HMF), - 5,5'-[oxy-bis(methylene)]bis-2-furfural (di-HMF), and - water, - wherein the total amount of water in the starting mixture is at least 50% by weight, based on in the total weight of the starting mixture, and - wherein the pH of the starting mixture is in the range of 4.0 to 7.0, (b) subjecting said starting mixture to oxidation conditions in the presence of a gas that contains the oxygen and a catalytically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support, such that the HMF and di-HMF react to provide the furan-2,5-dicarboxylic acid in a product mixture which also includes water.
[0002]
Process according to claim 1, characterized in that the starting mixture has a molar ratio of HMF to di-HMF in the range of 100 to 0.8, and/or the total weight of HMF and di-HMF in the mixture of starting mixture is in the range of 0.1 to 50% by weight, based on the total weight of the starting mixture.
[0003]
3. Process according to any one of claims 1 to 2, characterized in that the pH of the product mixture is less than 7.
[0004]
Process according to any one of claims 1 to 3, characterized in that said starting mixture at a temperature in the range of 70°C to 200°C is subjected to said oxidation conditions in the presence of said gas containing the oxygen and said catalystically effective amount of a heterogeneous catalyst comprising one or more noble metals on a support such that both HMF and di-HMF react to provide furan-2,5-dicarboxylic acid in the product mixture, also comprising water and oxidation by-products.
[0005]
A process according to any one of claims 1 to 4, characterized in that said starting mixture is subjected to said oxidation conditions in a pressurized reactor, wherein the partial pressure of oxygen in the reactor is, at least temporarily, in the range from 1 to 100 bar (0.1 MPa to 10 MPa) during the reaction of HMF and di-HMF to furan-2,5-dicarboxylic acid.
[0006]
6. PROCESS, according to any one of claims 1 to 5, characterized in that the total amount of acetate and acetic acid ions in said starting mixture is less than 10% by weight, wherein the total amount of carboxylic acid ions and the carboxylic acid in the starting mixture is less than 10% by weight.
[0007]
Process according to any one of claims 1 to 6, characterized in that the step of preparing said starting mixture comprises: (a1) preparing or supplying a mixture of material comprising: - one, two or more selected compounds from the group consisting of hexoses, oligosaccharides comprising hexose units and polysaccharides comprising hexose units, and (a2) subjecting said mixture of material to reaction conditions so that the resulting mixture comprises: - HMF - di-HMF and - water (a3) optionally subjecting the mixture resulting from step (a2) to additional treatment conditions, without the addition of a carboxylic acid and/or without the addition of an acid solvent to dissolve the HMF and di - HMF, - so that said starting mixture results.
[0008]
Process according to any one of claims 1 to 7, characterized in that, in said heterogeneous catalyst comprising one or more noble metals on a support: (i) at least one of said noble metals is selected from the group that consists of gold, platinum, iridium, palladium, osmium, silver, rhodium and ruthenium, and/or (ii) said support is selected from the group consisting of carbon, metal oxides, metal halides and metal carbides.
[0009]
Process according to any one of claims - to 8, characterized in that, in said heterogeneous catalyst comprising one or more noble metals on a support: - at least one of said noble metals is selected from the group consisting of platinum, iridium, palladium, osmium, rhodium and ruthenium, and - said support is carbon.
[0010]
Process according to any one of claims 1 to 9, characterized in that, in said heterogeneous catalyst comprising one or more noble metals on a support: - said one or one of said more noble metals is platinum and said support is carbon, and - the platinum content on the support is in the range of 0.1 to 20% by weight, based on the total weight of the heterogeneous catalyst comprising one or more noble metals on a support.
[0011]
Process according to any one of claims 1 to 10, characterized in that, in said heterogeneous catalyst comprising one or more noble metals on a support: - the molar ratio of said one or one of said more noble metals to an amount total HMF and di-HMF will be in the range of 1:1,000,000 to 1:10 and one or one of said nobler metals will be platinum.
[0012]
Process according to any one of claims 1 to 11, characterized in that the product mixture obtained in step (b) comprises furan-2,5-dicarboxylic acid in dissolved form and wherein the product mixture obtained in step (b) does not comprise furan-2,5-dicarboxylic acid in solid form.
[0013]
Process according to claim 3, characterized in that said pH of the product mixture is in the range of 1 to 4.
[0014]
Process according to claim 4, characterized in that said starting mixture is at a temperature in the range of 100°C to 135°C.
[0015]
15. PROCESS, according to claim 5, characterized in that said partial pressure of oxygen in the reactor is temporarily in the range of 1 to 20 bar (0.1 Mpa to 20 Mpa).
[0016]
Process according to claim 10, characterized in that said platinum content in the support is in the range of 1 to 10% by weight.
[0017]
17. USE OF A CATALYST, comprising one or more noble metals on a support, characterized by being as a heterogeneous oxidation catalyst to accelerate in an aqueous starting mixture the conversion of HMF and di-HMF to furan-2 acid, 5-dicarboxylic acid, wherein the pH of the starting mixture is in the range of 4.0 to 7.0.

类似技术:

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法律状态:
2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/07/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP15177884.2|2015-07-22|

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EP15177884|2015-07-22|

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PCT/EP2016/065494|WO2017012842A1|2015-07-22|2016-07-01|Process for preparing furan-2,5-dicarboxylic acid|

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