The present invention relates to a process for preparing a mixture comprising 5-(hydroxy- methyl)furfural (HMF) and one or more specific HMF esters. The invention also relates to a corresponding use of a specific carboxylic acid ester in such process. The present invention is defined in the appended claims. Furthermore, preferred configurations and aspects of the present invention are apparent from the detailed description and the working examples.

5-(Hydroxymethyl)furfural (HMF) and derivatives thereof are important intermediate compounds for production of various products, for example surfactants, polymers and resins.

With increasing depletion of fossil feedstocks, starting materials based on renewable resources are needed, e.g. as alternatives to terephthalic acid (a compound used in the production of polyethylene terephthalate, PET). PET is based on ethylene and p-xylene which are usually obtained starting from of oil, natural gas or coal, i.e. from fossil fuels. While bio-based routes to ethylene (e.g. dehydration of bio-ethanol) are operated on commercial scale a straightforward access to bio-terephthalic acid remains difficult. FDCA is the best bio-based alternative to terephthalic acid (for further information see: Lichten- thaler, F.W., "Carbohydrates as Organic Raw Materials" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010).

HMF is a versatile platform chemical. Alkoxymethylfurfurals, e.g. 2,5-furandicarboxylic acid, 5-hydroxymethylfuroic acid, bishydroxymethylfuran, 2,5-dimethylfuran, and the diether of HMF are furan derivatives with a high potential in fuel and/or polymer applications. Some important non-furanic compounds can also be produced from HMF, namely levulinic acid, adipic acid, 1 ,6-hexanediol, caprolactam, and caprolactone.

FDCA can be co-polymerized with mono-ethylene glycol to give polyethylene furanoate (PEF), a polyester with properties similar to PET.

FDCA is usually obtained starting from fructose and/or other hexoses via a catalyzed, preferably acid-catalyzed, dehydration to key intermediate 5-(hydroxymethyl)furfural (HMF) followed by oxidation to FDCA. In literature, processes are disclosed where esters of HMF are used as precursors to prepare FDCA (e.g. US 8,242,293 B2). monomeric . . . ..

hexose dehydration _;

molecules

HMF

In the dehydration step by-products are formed, depending on the specific design of the process.

Typical by-products of this process are levulinic acid and formic acid (see scheme below) which are formed upon hydrolysis of HMF.

In processes for preparing a mixture comprising 5-(hydroxymethyl)furfural (HMF) (and one or more by-products) or in processes for preparing FDCA known in the prior art, a mixture comprising 5-(hydroxymethyl)furfural (HMF) is prepared by subjecting a material mixture, comprising one, two or more compounds selected from the group consisting of hexoses (monomeric hexose molecules, e.g. fructose), oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, to reaction conditions so that a mixture comprising HMF, water and by-products (for example, levulinic acid and formic acid) results. Under the reaction conditions oligo- and/or polysaccharides are usually depolymerised, and subsequently the resulting monosaccharides, e.g. monomeric hexose molecules, are converted into HMF. Hexoses, oligosaccharides and polysaccharides are typically selected from the group consisting of fructose, glucose, and cellulose. During depolymerisation oligo- or polysaccharides are usually converted into monomeric hexose molecules by hydrolytic cleavage of the ether bonds connecting the different hexose units in an oligo- or polysaccharide molecule (e.g. cellulose). The products of a typical depolymerization process (monomeric hexose molecules) are present in their aldehyde form. Typically, according to routines at least in part previously undisclosed, depolymerization is conducted by using a catalyst, preferably in a one-pot-procedure. Typically a hydro- philic solvent is used (in particular water), e.g. in order to increase the amount of dissolved cellulose thus increasing the yield per process run. It is typically advantageous to conduct the conversion of cellulose into HMF by means of a heterogeneous catalyst in order to facilitate post-synthetic workup. In a typical depolymerization process, an aqueous solution is used as a solvent, sometimes comprising 50 wt.-% of water or more, based on the total weight of the depolymerization mixture used.

Alternatively, if monosaccharides are used as a starting material for preparing a mixture comprising HMF, water, and by-products, e.g. di-HMF (5,5'(oxy-bis(methylene))bis-2- furfural), no depolymerisation step is needed.

Monosaccharides produced or provided are typically subjected to a dehydration process, wherein the monomeric hexose molecule is typically transferred by isomerisation (via e.g. ketone-enone tautomerization) into its ketone form which is subsequently converted into its ring form. After ring closure, the formed ring-closed hexose molecules are typically dehydrated (and optionally further isomerised) resulting in a mixture comprising HMF, byproducts (e.g. di-HMF) and water. However, water causes undesirable by-products due to hydrolysis of the formed HMF as described above (for example, humins, levulinic acid and formic acid). Due to the insolubility of specific monomeric hexose molecules (e.g. fructose) in common organic solvents, a typical dehydration process step in the prior art is performed in an aqueous environment so that an aqueous solution comprising HMF and water is obtained as a (crude) mixture. As mentioned above, the presence of water leads to hydrolysis of HMF into by-products (e.g. levulinic acid and formic acid) and therefore decreases the overall yield of the reaction.

Isolation of HMF from such aqueous mixtures is challenging since HMF often undergoes side-reactions, e.g. hydrolysis (see scheme below).

Hence, the (crude) mixture comprising HMF and water is usually contaminated with byproducts to a certain degree and separation of HMF from the by-products is not possible with justifiable effort. The aforementioned disclosures regarding the depolymerization or dehydration step also apply to (i) a process for preparing a mixture comprising 5-(hydroxymethyl)furfural (HMF) and one or more HMF esters and a corresponding process for preparing furan-2,5- dicarboxylic acid comprising the step of further processing said mixture and (ii) a use of a carboxylic acid ester in a process for preparing 5-(hydroxymethyl)furfural and HMF esters according to the present invention as described in detail hereinbelow or for preparing FDCA according to the present invention as described in detail hereinbelow. In particular, the successive steps of depolymerization and dehydration can be used to prepare a mixture as employed according to the present invention.

Different teachings regarding the isolation or preparation of FDCA or HMF, respectively, have been reported in the patent literature:

WO 2008/054804 A2 relates to "Hydroxymethyl furfural oxidation methods" (title). It is disclosed that a high solubility of FDCA in an acetic acid/water mixture (volume ratio 40:60) is achieved, compared to the solubility in pure water (cf. paragraph [0058]). WO 2013/033081 A2 discloses a "process for producing both biobased succinic acid and 2,5-furandicarboxylic acid" (title).

US 2008/103318 discloses "hydroxymethyl furfural oxidation methods" (title) comprising the step of "providing a starting material which includes HMF in a solvent comprising water into reactor". The starting material is brought into contact "with the catalyst comprising Pt on the support material where the contacting is conducted at a reaction temperature of from about 50°C to about 200°C".

US 8,877,950 B2 relates to a "method for the synthesis of 5-hydroxymethylfurfural ethers and their use" (title). HMF derivatives are made "by reacting a fructose and/or glucose- containing starting material with an alcohol in the presence of a catalytic or sub- stoichiometric amount of solid ("heterogeneous") acid catalyst" (see abstract).

US 8,242,293 B2 relates to a "Method for the synthesis of organic acid esters of 5- hydroxymethylfurfural and their use" (title). The corresponding esters are disclosed to be "the condensation product of formic acid or its anhydride with HMF (formioxymethylfur- fural), acetic acid or its anhydride with HMF (5-acetoxymethylfurfural), or of propionic acid or its anhydride with HMF (5-propionoxymethylfurfural)" (see column 1 , lines 20 - 24) or of "(iso)-butyric acid" (see column 2, line 43) or of„(iso)butyric anhydride" (see column 2, line 47). Different catalysts have been employed in a corresponding process (see column 3, lines 1 - 31 ). WO 2009/076627 A2 relates to the "conversion of carbohydrates to hydroxy- methylfurfural (HMF) and derivatives" (title). A method is disclosed "for synthesizing HMF by contacting a carbohydrate source with a solid phase catalyst" (see claim 1 ). Furthermore, a method of preparing HMF esters is disclosed starting from a mixture "comprising a carbohydrate source, a carboxylic acid, with or without an added catalyst to provide a reaction mixture" (see claim 4).

WO 201 1/043661 A1 relates to a "Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid" (title). A method is disclosed "for the preparation of 2,5-furan dicarboxylic acid comprising the step of contacting a feed comprising a compound selected from the group consisting of 5- hydroxymethylfurfural ("HMF"), an ester of 5-hydroxymethylfurfural, 5-methylfurfural, 5- (chloromethyl)furfural, 5-methylfuroic acid, 5-(chloromethyl)furoic acid, 2,5-dimethylfuran and a mixture of two or more of these compounds with an oxidant in the presence of an oxidation catalyst at a temperature higher than 140 °C"(see abstract). The oxidation catalyst comprises cobalt, manganese and/or a source of bromine (see claims 3 and 4).

WO 2009/030512 A2 relates to "hydroxymethylfurfural ethers and esters prepared in ionic liquids" (title). A method is disclosed "for the manufacture of an ether or ester of 5- hydroxymethylfurfural by reacting a hexose-containing starting material or HMF with an alcohol or an organic acid dissolved into an ionic liquid, using a metal chloride as catalyst" (see claiml ).

WO 2013/087614 A1 relates to a process for preparing 5-hydroxymethylfurfural (HMF), characterized in that a) solutions (called starting solution hereinafter) comprising one or more saccharides and an organic solvent having a boiling point greater than 200°C (at standard pressure) (called high boiler for short) and water and a solvent having a boiling point greater than 60°C and less than 200°C (at standard pressure, called low boiler for short) are supplied to a reaction vessel, b) a conversion of the hexose to HMF in the presence of steam with simultaneous distillative removal of the HMF is effected in the reaction vessel and c) the distillate obtained is an aqueous, HMF containing solution (see abstract). The low boiler can be EtOAc. The skilled person understands that the low boiler is not used as a solvent for the saccharide but as an agent for evaporating the product from the high boiler. Correspondingly, in an example using EtOAc this low boiler is present only in an amount of less than 50 wt.-% (see page 29, table 1 , entry 8). The fact that the starting solution is contacted with vaporized low boiler primarily acting as a stripping agent for HMF and not as a solvent for the saccharide, is apparent from "Fig 1 ", "Fig 2" as well as "Fig 3" and in particular from the fact that the treatment of the starting solutions with the low boiler is conducted at reduced pressures (see page 13, paragraph 2). Furthermore, WO 2013/087614 A1 discloses the usage of acids as catalysts. KR 201 10079484 A according to its published abstract relates to a method for preparing hydroxymethyl furfural from starch or plant organism biomass. The preparation method comprises forming a first mixture of ionic liquid and organic solvent catalyst and then adding a metal catalyst agent, reacting the mixture at 100-150 °C for 5-20 minutes, adding the acid catalyzer and starch or plant organism extracts, and heating the reaction mixture at 100-120 °C for 50-100 minutes. A preferred organic solvent catalyst that is present together with the acid catalyst is 5-20% ethyl acetate.

WO 2015/075540 A1 relates to a process for synthesis of furan derivative using an acid catalyst in monophasic organic solvent (see [0001 ]). The furan derivative can be 5-HMF (see [0002]). The overall process employs use of monophasic organic solvents (low boiling, or high boiling) (see [0091]). The monophasic organic solvent in one implementation is selected from the group consisting of alcohols with the formula R-OH, N, N- Dimethyl formamide, Dimethyl sulfoxide, esters, and 1 , 4-dioxane, see [0034]. In the examples, specific alcohols, Dimethyl sulfoxide, and N, N-Dimethyl formamide are used, as solvents, but no esters.

WO 2009/155297 A1 relates to methods for chemical transformation of sugars and cellu- losic biomass into fuels and chemicals in substantial yields under moderate conditions (see [0003]). Despite the considerable efforts made by industry, there remains a need for further improvement. Thus, according to a first aspect it was an object of the present invention to provide an improved process for preparing a mixture comprising 5-(hydroxymethyl)furfural (HMF) and one or more HMF esters and to provide a process for preparing furan-2,5- dicarboxylic acid (FDCA), which avoid or at least alleviates disadvantages of the proc- esses known to date (and as stated above) and which can be operated in an economically advantageous manner. Preferred processes to be specified according to further aspects should favourably be capable to be conducted without the use of a dehydration catalyst and/or initial addition of acid, - reuse by-products formed in the process, prevent side reactions, increase the yield of the overall process compared to processes known in the prior art, allow for a more convenient separation of by-products compared to processes known in the prior art, and/or allow to reduce the complexity of reactor set-ups known in the prior art. According to the invention with respect to the object of preparing a mixture comprising 5- (hydroxymethyl)furfural (HMF) and one or more HMF esters, this is achieved by

(a) a process for preparing a mixture comprising 5-(hydroxymethyl)furfural (HMF) and one or more HMF esters of formula (I),

(I) wherein in each of said HMF esters of formula (I), independently of each other, R1 is

(i) hydrogen or

(ii) a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, the process comprising the following steps:

(A-1 ) preparing or providing a starting mixture comprising one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, and as the solvent or as a co-solvent for said carbohydrate compounds an amount of one or more carboxylic acid esters of formula (II) O

II

R1 c R2

O

(II), in in each of said carboxylic acid esters of formula (II)

R1 is the same as defined for formula (I) above and

R2 is a substituted or unsubstituted, branched or linear or cyclic, aliphatic hydrocarbon radical having a total number of 10 carbon atoms or less, subjecting said starting mixture to reaction conditions so that at least one of said one, two or more carbohydrate compounds reacts, and a fraction of said amount of one or more carboxylic acid esters of formula (II) is hydrolyzed, so that a mixture results comprising

5-(hydroxymethyl)furfural and/or said one or more HMF esters of formula (I), one or more carboxylic acids of formula (III)

O II

c

R1 OH

(Hi), wherein R1 is the same as defined for formula (I) above,

- one or more alcohols R2-OH, wherein R2 is the same as defined for formula (II) above, and

- a remaining fraction of said amount of one or more carboxylic acid esters of formula (II), wherein the starting mixture prepared or provided in step (A-1 ) comprises a total amount of carboxylic acid esters of formula (II) of at least 50 wt.-%, based on the total weight of the starting mixture

With respect to the object of providing a process for preparing FDCA, this is achieved by

(b) a process for preparing furan-2,5-dicarboxylic acid, comprising:

(A) conducting a process for preparing a mixture comprising 5-(hydroxymethyl)furfural (HMF) and one or more HMF esters of formula (I),

(I) wherein in each of said HMF esters of formula (I), independently of each other, R1 is

(i) hydrogen or

(ii) a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, the process for preparing said mixture comprising the following steps: (A-1 ) preparing or providing a starting mixture comprising one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, and as the solvent or as a co-solvent for said carbohydrate compounds an amount of more carboxylic acid esters of formula (II)

(II), wherein in each of said carboxylic acid esters of formula (II)

R1 is the same as defined for formula (I) above and

R2 is a substituted or unsubstituted, branched or linear or cyclic, aliphatic hydrocarbon radical having a total number of 10 carbon atoms or less, subjecting said starting mixture to reaction conditions so that at least one of said one, two or more carbohydrate compounds reacts, and a fraction of said amount of one or more carboxylic acid esters of formula (II) is hy- drolyzed, so that a mixture results comprising

5-(hydroxymethyl)furfural and/or said one or more HMF esters of formula (I), one or more carboxylic acids of formula (III)

O II

c-

R1 ΌΗ

(Hi), wherein R1 is the same as defined for formula (I) above,

- one or more alcohols R2-OH, wherein R2 is the same as defined for formula (II) above, and

- a remaining fraction of said amount of one or more carboxylic acid esters of formula (II),

(B) preparing furan-2,5-dicarboxylic acid by further processing said mixture resulting in step (A-2), said further processing preferably comprising the step of

(B-1 ) subjecting said mixture resulting in step (A-2) or a mixture comprising 5-(hydroxymethyl)furfural and/or one or more HMF esters of formula (I) obtained from said mixture resulting in step (A-2) by additional treatment steps to oxidation conditions so that a product mixture results comprising furan-2,5- dicarboxylic acid and one or more carboxylic acids of formula (III) wherein the starting mixture prepared or provided in step (A-1 ) comprises a total amount of carboxylic acid esters of formula (II) of at least 50 wt.-%, based on the total weight of the starting mixture.

Summarizing both processes of the present invention as defined and described above, the present invention relates to a process for (A) preparing a mixture comprising 5- (hydroxymethyl)furfural (HMF) and one or more HMF esters of formula (I),

(I) wherein in each of said HMF esters of formula (I), independently of each other, R1 is

(i) hydrogen or

(ii) a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, the process comprising the following steps:

(A-1 ) preparing or providing a starting mixture comprising one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccha- rides comprising hexose units, and as the solvent or as a co-solvent for said carbohydrate compounds an amount of one or more carboxylic acid esters of formula (II)

(II), wherein in each of said carboxylic acid esters of formula (II)

R1 is the same as defined for formula (I) above and

R2 is a substituted or unsubstituted, branched or linear or cyclic, aliphatic hydrocarbon radical having a total number of 10 carbon atoms or less,

(A-2) subjecting said starting mixture to reaction conditions so that at least one of said one, two or more carbohydrate compounds reacts, and a fraction of said amount of one or more carboxylic acid esters of formula (II) is hy- drolyzed, so that a mixture results comprising

5-(hydroxymethyl)furfural and/or said one or more HMF esters of formula (I), one or more carboxylic acids of formula (III) _R1 ^/C -OH

(Hi), wherein R1 is the same as defined for formula (I) above,

- one or more alcohols R2-OH, wherein R2 is the same as defined for formula (II) above, and

- a remaining fraction of said amount of one or more carboxylic acid esters of formula (II) wherein the starting mixture prepared or provided in step (A-1 ) comprises a total amount of carboxylic acid esters of formula (II) of at least 50 wt.-%, based on the total weight of the starting mixture.

In a process according to the invention as described above or below, carboxylic acid esters of formula (II) in step (A-1 ) is present as the solvent or as a co-solvent for said carbohydrate compounds, in step (A-2) a fraction of said amount of one or more carboxylic acid esters of formula (II) is hydrolyzed. Thus, in a process according to the invention as described above or below, carboxylic acid esters of formula (II) have the function of a "reactive solvent". A reactive solvent acts as both (i) a reactant and (ii) a solvent. As a reactant, in step (A-2) the carboxylic acid esters of formula (II) react with water (formed in-situ or present in the starting mixture of step (A-1 )) to form carboxylic acids of formula (III) which can then further react with HMF to form HMF esters of formula (I). As a (co- solvent, in steps (A-1 ) and (A-2) the carboxylic acid esters of formula (II) contribute to keeping in solution said one, two or more carbohydrate compounds, in the starting mixture. Furthermore, the remaining fraction of carboxylic acid esters of formula (II) typically contributes to keeping in solution the products (HMF and/or HMF esters of formula (I)) present in the mixture resulting in step (A-2). Typically and preferably, the carboxylic acid esters of formula (II) in the starting mixture prepared or provided in step (A-1 ) are present as a constituent of a liquid phase, in order to be an effective "solvent" or "co-solvent" for the carbohydrate compounds. Typically and preferably, the starting mixture as defined above is a mixture (solution) which is present in the condensed, preferably liquid, phase, or is a suspension comprising a liquid phase, and suspended therein solid matter.

In many industrial cases, it is preferred to employ alkyl formates of the formula R2-0- C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is a hydrocarbon radical as defined herein above or below (as for alternative (ii)), the corresponding carboxylic acid esters of formula (II) are preferred over said alkyl formates of the formula R2-0-C(=0)H.

In particular, in each specific aspect of the present invention and all statements regarding preferred embodiments or features, group R1 is the same in the compounds of formula (I), (II) and (III). The meaning of R1 may differ for different specific aspects and all statements regarding preferred embodiments or features of the present invention.

Similarly, in each specific aspect of the present invention and all statements regarding preferred embodiments or features, group R2 is the same in the compounds of formula (II) and alcohol R2-OH. The meaning of R2 may differ for different specific aspect and all statements regarding preferred embodiments or features of the present invention.

If not indicated otherwise, the "total number" of carbon atoms in a specified radical is the total number in the radical including any substituents. I.e., when counting the total number of carbon atoms in a substituted radical the carbon atoms in the substituent are also counted. In step (A-2), the term "reaction conditions" indicates conditions causing

(a) said carbohydrate compounds to react so that 5-(hydroxymethyl)furfural (HMF) and/or (by reaction of HMF) said one or more HMF esters of formula (I) are generated and (b) hydrolysis of a fraction of said amount of one or more carboxylic acid esters of formula (II) so that said carboxylic acids of formula (III) and said alcohols R2-OH are formed. The reaction mechanism involved is described in more detail below, in particular with reference to exemplary processes.

As stated above, dehydration of fructose is often conducted in an aqueous medium. Beside the intrinsic problem of conducting dehydration reactions in aqueous media, water can lead to several by-products (see for example Tian et al., Chem. Commun., 2013, 49, pages 8668 - 8670). As water is produced in the dehydration of fructose to HMF, even under initially non-aqueous reaction conditions, the water content increases with reaction time. The challenges and problems of prior art process are summarized in, e.g. EP 2 762 470 A1 which relates to "the synthesis and recovery of substantially pure HMF and deriv- atives thereof from hexose carbohydrate feedstocks" (see [0002]). The document explicitly mentions that "a method which provides HMF with good selectivity and in high yields has yet to be found" and which does not yield "by-products, such as, levulinic and formic acids" (see [0008]). In contrast thereto, a process according to the present invention produces HMF and HMF esters of formula (I) with high selectivities and low by-product formation. In a process according to the present invention carboxylic acid esters of formula (II) act and are deliberately used as a dehydration agent which reacts with water, resulting in the formation of one or more carboxylic acids of formula (III) and one or more alcohols R2-OH (see, for example, the corresponding reaction in Fig. 1 ).

Moreover, concurrent with the reaction of carbohydrate compounds to HMF and/or HMF esters of formula (I) in the presence of one or more carboxylic acid esters of formula (II), one or more carboxylic acids of formula (III) (see step (A-2)) are produced which act as a solvent in a subsequent oxidation step (B-1 ).

Under the reaction conditions of step (A-2) said one or more carboxylic acid esters of formula (II) react with water (present in the starting mixture prepared or provided in step (A-1 ) and/or produced by the dehydration of carbohydrate compounds in step (A-2)) to give one or more carboxylic acids of formula (III) and one or more alcohols R2-OH. Thus, the negative effect of the side reactions typically caused by the presence of water (see the above discussion of prior art processes) is avoided or at least alleviated.

The reaction products of the reaction of said one or more carboxylic acid esters of formu- la (II) with water, i.e. said carboxylic acid of formula (III) and the alcohol R2-OH, surprisingly do not cause disadvantageous side reactions as observed for water, and thus contribute to an increase of the overall yield in HMF, HMF esters of formula (I) and, if applicable, FDCA in comparison to processes of the prior art. Alcohol R2-OH as well as carboxylic acid esters of formula (II) are also more conveniently separated from the mixture resulting in step (A-2) than, for example, water.

The formation of HMF esters of formula (I) is advantageous since it protects the hydroxyl group of the HMF and thus prevents dimerization or even polymerization of HMF (leading to humins). Furthermore, HMF esters of formula (I) can be oxidized to FDCA in the same manner as HMF.

The carboxylic acids of formula (III) formed in the process of the invention serve as (co- solvents for the carbohydrate compounds in step (A-2). Thus, in contrast to the prior art, in processes according to the present invention organic acids or other corrosive com- pounds, typically used as solvents, do not need to be initially present in the starting mixture prepared or provided in step (A-1 ), and do not need to be added in a separate step. Therefore, no storage units or additional handling of these corrosive compounds is necessary.

Preferred are processes of the present invention as described herein above or below, wherein in the mixture resulting in step (A-2) the total amount of 5-(hydroxymethyl)furfural and HMF esters of formula (I) is in the range of from 0.5 to 50 wt.-%, preferably in the range of from 1 to 40 wt.-%, more preferably in the range of from 5 to 30 wt.-%, based on the total weight of the mixture resulting in step (A-2).

The upper limit for the total amount of 5-(hydroxymethyl)furfural and HMF esters of for- mula (I) is determined by their maximum solubility in carboxylic acid esters of formula (II).

If in the mixture resulting in step (A-2) the total amount of 5-(hydroxymethyl)furfural and HMF esters of formula (I) is below the lower limit of the ranges as indicated, the overall process can hardly be conducted in an efficient and economic manner.

Processes of the present invention as described above or below (or as described above as being preferred) are preferred, wherein the total weight of the one, two or more carbohydrate compounds in the starting mixture prepared or provided in step (A-1 ) is in the range of from 1 to 70 wt.-%, preferably in the range of from 5 to 60 wt.-%, more preferably in the range of from 10 to 50 wt.-%, based on the total weight of the starting mixture.

If the total weight of the one, two or more carbohydrate compounds in the starting mixture prepared or provided in step (A-1 ) is above the upper limit of the ranges as indicated, by- product formation becomes increasingly troublesome. If the total weight of the one, two or more carbohydrate compounds in the starting mixture prepared or provided in step (A-1 ) is below the lower limit of the ranges as indicated, the overall process can hardly be conducted in an efficient and economic manner. In particular, processes of the present invention as described above or below are preferred, wherein the starting mixture prepared or provided in step (A-1 ) comprises fructose and glucose.

Fructose and glucose are preferred carbohydrate compounds in the starting mixture prepared or provided in step (A-1 ) as they are monomeric hexoses and thus do not need to be depolymerised as, for example, oligosaccharides comprising hexose units, or polysaccharides comprising hexose units.

Also preferred are processes of the present invention as described above or below wherein the starting mixture prepared or provided in step (A-1 ) does not comprise NH ₄ CI.

If NH ₄ CI is used in a process according to the present invention side-product formation is observed, e.g. formation of 5-(chloromethyl)furfural.

In particular, processes of the present invention as described above or below are preferred, wherein the starting mixture prepared or provided in step (A-1 ) does not comprise any protic chloride salt.

Protic chloride salts often have the disadvantage of causing side-product formation as in the case of NH ₄ CI above. This may cause side-product formation and thus may lower the yield of the overall reaction.

In many cases, processes of the present invention as described above or below are preferred, wherein the starting mixture prepared or provided in step (A-1 ) does not comprise any protic nitrogen-containing cation. Protic nitrogen-containing cations often have the disadvantage of causing side-product formation as in the case of NH ₄ CI above. This may cause side-product formation and thus may lower the yield of the overall reaction. Preferred are processes of the present invention as described above or below, wherein the starting mixture prepared or provided in step (A-1 ) does not comprise any protic halide salt.

Similarly, as explained for protic chloride salts, protic halide salts in general often have the disadvantage of causing side-product formation. These acids cause side-product formation and thus lower the yield of the overall reaction.

Preferred are processes of the present invention as described above or below, wherein the mixture resulting in step (A-2) does not comprise 5-(chloromethyl)furfural in an amount of 1 wt% or more. Preferably, the mixture resulting in step (A-2) does not comprise any 5-(chloromethyl)furfural.

The skilled person limits or avoids the formation of 5-(chloromethyl)furfural by limiting or avoiding the presence of any protic chloride salt, preferably by limiting or avoiding the presence of chloride in the starting mixture prepared or provided in step (A-1 ). Under reaction conditions as in step (A-2) of the present invention, 5-(chloromethyl)furfural reacts with HMF forming HMF dimers (5,5'(oxy-bis(methylene))bis-2-furfural) thus decreasing the yield in HMF or HMF esters of formula (I) in step (A-2) of the present invention.

Preferred are processes of the present invention as described above or below, wherein the starting mixture prepared or provided in step (A-1 ) comprises less than 35 wt% of water, preferably less than 20 wt% of water, more preferably less than 10 wt% of water, even more preferably less than 1 wt% of water, most preferably less than 0.1 wt% of water, based on the total weight of the starting mixture. It is advantageous if the starting mixture prepared or provided in step (A-1 ) comprises only a small amount of water which is consumed by directly hydrolysing said carboxylic acid esters of formula (II) and thus does not cause any disadvantageous side-reaction as in prior art processes discussed above. Preferred are processes of the present invention as described above or below, wherein the starting mixture prepared or provided in step (A-1 ) has an acid value below 50, preferably below 5, more preferably below 1.

In a process of the invention, no acid needs to be added to the starting mixture prepared or provided in step (A-1 ) and thus no storage units or additional handling of these corro- sive compounds is necessary.

Correspondingly, preferred are processes of the present invention as described above or below, wherein the total concentration of Br0nsted acids in the starting mixture prepared or provided in step (A-1 ) is lower than 0.15 mol/L, preferably lower than 0.1 mol/L, even more preferably lower than 0.05 mol/L, most preferably lower than 0.01 mol/L. However, due to e.g. disproportionation a very small amount of Br0nsted acid might be inevitably present in the starting mixture.

In a process of the invention, no Bransted acid needs to be present in or added to the starting mixture prepared or provided in step (A-1 ) to obtain the products in high yields. Thus, the purification of the products is facilitated and the process of the invention is more environmentally sustainable and advantageous with respect to occupational safety.

In a process of the invention, preferably no heterogeneous acid catalyst is employed.

In a process of the invention, preferably no aliphatic or aromatic sulfonic acid is employed.

Preferred are processes of the present invention as described above or below, wherein in the mixture resulting in step (A-2) the molar ratio of the amount of 5-(hydroxy- methyl)furfural to the total amount of HMF esters of formula (I) is in the range of from 100 to 0.001 , preferably in the range of from 50 to 0.05, more preferably in the range of from 10 to 0.1. The person skilled in the art identifies the corresponding reaction conditions by, e.g., a small series of pre-experiments. For example, in such a series of pre-experiments, he changes the reaction temperature (and/or reaction time) and measures the ratio of HMF to the total amount of HMF esters of formula (I) in the resulting product mixture. In mixtures resulting in step (A-2) with a molar ratio of the amount of 5-(hydroxy- methyl)furfural to the total amount of HMF esters of formula (I) as described above, less by-products are formed in a oxidation reaction in a subsequent step (B-1 ).

Preferred are processes of the present invention as described above or below, wherein in step (A-2) the reaction temperature is for at least 10 minutes in the range of from 70°C to 300°C, preferably in the range of from 140°C to 260°C, more preferably in the range of from 160°C to 240°C, even more preferably in the range of from 185°C to 220°C and/or wherein in step (A-2) the reaction temperature is in the range of from 185°C to 220°C for at least 10 minutes, preferably for at least 30 min, more preferably for at least 1 hour.

It has been reported in literature (Jing and Xiuyang, Chin. J. Chem. Eng., Vol. 16, No. 6, 2008, page 893) that in glucose decomposition in aqueous media the "maximum yield of 5-HMF reached 32.0% in 30 min" (see section 3.4) and "5-HMF further degraded to formic acid, levulinic acid, and humic matter" (see section "conclusion"). However, in a process according to the present invention, the side reaction caused by water is reduced or prevented even if the reaction time is as short as 10 minutes. Particularly, processes of the present invention as described above or below are preferred, wherein said one or at least one, preferably all, of said more alcohols R2-OH

(i) has a vapor pressure of at least 0.1 kPa at 25 °C, preferably at least 1 kPa at 25 °C, more preferably at least 3.2 kPa at 25 °C, even more preferably at least 4 kPa at 25 °C, particularly more preferably at least 5kPa at 25 °C and/or

(ii) is selected from the group consisting of: methanol(R2 = CH ₃ ),

ethanol (R2 = CH ₂ CH ₃ ),

- 1-propanol (R2 = CH ₂ CH ₂ CH ₃ ),

2-propanol (R2 = CH(CH ₃ ) ₂ ,

1- butanol (R2 = CH ₂ CH ₂ CH ₃ ),

2- butanol (R2 = CH(CH ₃ )CH ₂ CH ₃ ),

1-hydroxy-2-methylpropan (R2 = CH ₂ CH(CH ₃ ) ₂ ),

- 2-hydroxy-2-methylpropan (R2 = C(CH ₃ ) ₃ ),

and

2-Methoxyethanol (R2 = CH ₂ CH ₂ OCH ₃ ).

Specific alcohols R2-OH as described in the specific aspect above are particularly conveniently separated from the mixture resulting in step (A-2) due to their relatively low vapour pressures.

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R2 is the very same in the compounds of formula (II) and alcohol R2-OH.

Due to the intrinsic chemistry of a process of the invention, group R2 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in alcohol R2-OH.

Processes of the present invention as described above or below are preferred, wherein R1 is (i) hydrogen or

(ii) a linear or branched, saturated or unsaturated hydrocarbon radical having 15 carbon atoms or less, more preferably a linear or branched, saturated or unsaturated hydrocarbon radical having 8 carbon atoms or less, even more preferably a linear or branched, aliphatic radical having 6 carbon atoms or less, particularly more preferably -CH ₃ , -CH ₂ CH ₃ , -CH(CH ₃ ) ₂ , -C(CH ₃ ) ₃ , -CH ₂ CH ₂ CI-I ₃ , or -CH ₂ CH ₂ CH ₂ CH ₃ , most preferably -CH ₃ .

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III). In a process of the present invention, the specific meaning of R1 as defined according to this aspect is preferred as the corresponding carboxylic acids of formula (III) can be conveniently separated (e.g. by means of distillation) from FDCA or from a mixture comprising 5-(hydroxymethyl)furfural (HMF) and one or more HMF esters of formula (I) in a purification step (e.g. a distillation step). In many industrial cases, it is preferred to employ alkyl formates of the formula R2-0- C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is a hydrocarbon radical as defined herein above or below (as for alternative (ii)), the corresponding specific carboxylic acid esters of formula (II) as defined in the specific aspect above are preferred over said alkyl formates of the formula R2-0- C(=0)H. Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I).

Correspondingly, said one or at least one, preferably all, of said more carboxylic acids of formula (III)

O I I

_R1 - ^C -OH

(III) is preferably selected from the group consisting of:

- formic acid (R1 = H); preferred in specific industrial cases,

- acetic acid (R1 = CH ₃ ),

- propanoic acid (R1 = CH ₂ CH ₃ ),

- butanoic acid (R1 = CH ₂ CH ₂ CH ₃ ),

- 2-methylpropanoic acid (R1 = CH(CH ₃ ) ₂ ),

- 2,2-dimethylpropanoic acid (R1 = C(CH ₃ ) ₃ ),

and

- pentanoic acid (R1 = CH ₂ CH ₂ CH ₂ CH ₃ ), is more preferably selected from the group consisting of:

- acetic acid (R1 = CH ₃ ),

- propanoic acid (R1 = CH ₂ CH ₃ ),

- butanoic acid (R1 = CH ₂ CH ₂ CI-I ₃ ),

- 2-methylpropanoic acid (R1 = CH(CH ₃ ) ₂ ),

- 2,2-dimethylpropanoic acid (R1 = C(CH ₃ ) ₃ ),

and

- pentanoic acid (R1 = CH ₂ CH ₂ CH ₂ CH ₃ ), and most preferably said one or at least one of said more carboxylic acids of formula (III) acetic acid (R1 = CH ₃ ). As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III).

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I).

In many cases, processes of the present invention as described above or below are preferred, wherein in said one or at least one or preferably all of said more carboxylic acid esters of formula (II) - R1 is

(i) hydrogen (preferred in specific industrial cases) or

(ii) a linear or branched, saturated or unsaturated hydrocarbon radical having 15 carbon atoms or less, more preferably a linear or branched, saturated or unsaturated hydrocarbon radical having 8 carbon atoms or less, even more preferably a linear or branched, aliphatic radical having 6 carbon atoms or less, and independently thereof - R2 is a substituted or unsubstituted, branched or linear or cyclic, alkyl radical having a total number of 10 carbon atoms or less, preferably a substituted or unsubstituted, branched or linear or cyclic, alkyl radical having a total number of 6 carbon atoms or less, more preferably a unsubstituted alkyl radical selected from the group consisting of methyl, ethyl, prop-1 -yl, propan-2-yl, butan-1-yl, butan-2-yl, pentan-1 -yl, pentan-2-yl, pentan-3-yl, 2-methylpropan-1-yl, 2-methylpropan-2-yl, 2- methylbutan-1-yl, 3-methylbutan-1-yl, 2-methylbutan-2-yl, 3-methylbutan-2-yl, cyclopentyl, and cyclohexyl, even more preferably methyl.

In some industrial cases, it is preferred to employ alkyl formates of the formula R2-0- C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is a hydrocarbon radical as defined herein above or below (as for alternative (ii)), the corresponding specific carboxylic acid esters of formula (II) as defined in the specific aspect above are preferred over said alkyl formates of the formula R2-0- C(=0)H.

Carboxylic acid esters of formula (II) as defined above for this specific aspect are preferred as they are readily available and have a relatively low vapor pressure. Such car- boxylic acid esters of formula (II) with a low vapor pressure can be conveniently separated after step (A-2) from the mixture resulting in step (A-2), e.g. by means of distillation.

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III). Similarly, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R2 is the very same in the compounds of formula (II) and alcohol R2-OH.

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I), and similarly group R2 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in alcohol R2-OH.

Moreover, processes of the present invention as described above or below are particularly preferred, wherein said one or at least one, preferably all, of said more carboxylic acid esters of formula (II) is selected from the group consisting of methyl formate, ethyl formate, butyl formate methyl acetate, ethyl acetate, and butyl acetate, preferably selected from the group consisting of methyl acetate, ethyl acetate, and butyl acetate, more preferably methyl acetate.

Carboxylic acid esters of formula (II) as defined above for this specific aspect are particularly preferred as they are readily available and have a relatively low vapor pressure. Such carboxylic acid esters of formula (II) with a low vapor pressure can be conveniently separated after step (A-2) from the mixture resulting in step (A-2), e.g. by means of distillation.

In some industrial cases it is preferred to employ alkyl formates of the formula R2-0- C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is hydrocarbon radical as defined herein above or below (as for alternative (ii)), the corresponding specific carboxylic acid esters of formula (II) as defined in the specific aspect above are preferred over said alkyl formates of the formula R2-0- C(=0)H.

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III). Similarly, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R2 is the very same in the compounds of formula (II) and alcohol R2-OH.

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I), and similarly group R2 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in alcohol R2-OH.

Processes of the present invention as described above or below are preferred, wherein said one or at least one, preferably all, of said more HMF esters of formula (I) is 5- (formoxymethyl)furfural (R1 is hydrogen) or 5-(acetoxymethyl)furfural (R1 is methyl), preferably 5-(acetoxymethyl)furfural (R1 is methyl).

In some industrial cases it is preferred to employ alkyl formates of the formula R2-0- C(=0)H (as for alternative (i), meaning R1 = H) in the starting mixture prepared or provided in step (A-1 ) as they are readily available, and correspondingly 5- (formoxymethyl)furfural (R1 is hydrogen) is a preferred HMF ester of formula (I) produced in step (A-2). However, in other cases, where R1 is a hydrocarbon radical as defined herein above or below (as for alternative (ii), the corresponding specific carboxylic acid esters of formula (II) as defined in the specific aspect above are preferred over said alkyl formates of the formula R2-0-C(=0)H.

5-(Acetoxymethyl)furfural is a preferred HMF ester of formula (I) as it can be oxidized conveniently to FDCA in a similar manner as HMF.

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III).

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I).

Processes of the present invention as described above or below are also preferred, wherein in step (A-2) said starting mixture is subjected to said reaction conditions in a pressurized reactor, wherein preferably the pressure in the reactor at least temporarily is in the range of from 1 to 100 bar, preferably in the range of from 1 to 50 bar, more preferably in the range of from 1 .1 to 50 bar, most preferably in the range of from 3 to 29 bar.

Subjecting said starting mixture in step (A-2) to said reaction conditions mixture in step (A-2) in a pressurized reactor is preferred as higher reaction temperatures can be reached in a pressurized reactor and thus the reaction accelerated.

Furthermore, processes of the present invention as described above or below are preferred, wherein the molar ratio of the total amount of said carboxylic acid esters of formula (II) present in the starting mixture prepared or provided in step (A-1 ) to the total amount of water (i) present in the starting mixture prepared or provided in step (A-1 ) and

(ii) produced in step (A-2) by reaction of said carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units is above 1 , preferably above 1.2.

Starting mixtures prepared or provided in step (A-1 ) having a molar ratio of the total amount of said carboxylic acid esters of formula (II) to the total amount of water present in (i) and produced in (ii) of more than 1 prevent or at least reduce the hydrolysis of HMF to levulinic and formic acid because all the water is reacted with said carboxylic acid esters of formula (II).

Processes of the present invention as described above or below are preferred, wherein the mixture resulting in step (A-2) is non-aqueous or in the mixture resulting in step (A-2) the molar ratio of the total amount of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II) to water is above 1.

Preferably, the non-aqueous mixture resulting in step (A-2) comprises less than 0.1 wt% of water, based on the total weight of the mixture. Mixtures resulting in step (A-2), which have a molar ratio of the total amount of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II) to the total amount of water of more than 1 , prevent or reduce the hydrolysis of HMF to levulinic and formic acid as all the water (present in (i) and produced in (ii)) is further reacted with said carboxylic acid esters of formula (II). Moreover, the remaining fraction after step (A- 2) can be used for preparing a starting mixture as in step (A-1 ).

Processes of the present invention as described above or below are preferred, wherein said starting mixture prepared or provided in step (A-1 ) comprises water, wherein (in said starting mixture) the molar ratio of the total amount of said carboxylic acid esters of formula (II) to water is above 3, preferably above 5.

Aqueous starting mixtures prepared or provided in step (A-1 ), which have a molar ratio of the total amount of said carboxylic acid esters of formula (II) to water of more than 1 , prevent or reduce the hydrolysis of HMF to levulinic and formic acid because all the water present is further reacted with said carboxylic acid esters of formula (II).

Preferably, processes of the present invention as described above or below are processes, wherein said starting mixture prepared or provided in step (A-1 ) comprises water, wherein in said starting mixture the molar ratio of the total amount of said carboxylic acid esters of formula (II) to the sum of the total amount of water plus (ii) three times the total amount of hexoses and hexose units is above 1 , preferably above 1.2.

In a starting mixture prepared or provided in the dehydration step (A-1 ), three water molecules are produced per hexose unit. Therefore, the hydrolysis of HMF to levulinic and formic acid can only be prevented if all the water present (i) and in-situ produced (ii) further reacts with said carboxylic acid esters of formula (II).

Processes of the present invention as described above or below comprising the following step are preferred: in step (A-1 ) preparing said starting mixture by mixing - an aqueous feed mixture comprising said one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, with said one or more carboxylic acid esters of formula (II). Mixtures comprising carbohydrate compounds typically are aqueous. As the water contained in said mixtures comprising carbohydrate compounds can cause disadvantageous side-reactions as described above in prior art processes said water had to be separated from said mixtures comprising carbohydrate compounds. Thus, it is an achievement of the present invention that an aqueous starting mixture can be provided or prepared in step (A-1 ) and subjected to reaction conditions in step (A-2), without causing any disadvantages.

Processes of the present invention as described above or below are preferred, wherein none of said one or more carboxylic acid esters of formula (II) is ethyl oxalate, ethyl maleate, ethyl levulinate, methyl oxalate, methyl maleate or methyl levulinate. Furthermore, processes of the present invention as described above or below are preferred, wherein the starting mixture prepared or provided comprises a catalytically effec- tive amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI

and

NaBr.

A preferred catalytically effective amount of catalyst is a total amount of 20 ppm or more of said catalysts by weight based on the total weight of said one, two or more carbohydrate compounds in the reaction mixture of step (A-2).

Alkali halides as described above catalyze the formation of HMF and do not lead to side- product formation (e.g. 5-(chloromethyl)furfural or furfural) as it is observed when using NH ₄ CI as a catalyst.

Particularly preferred is a process according to the present invention as described above or below, wherein said one or more carboxylic acid esters of formula (II)

O II

R1 O

(II) present in said starting mixture prepared or provided in step (A-1 ) is prepared in a separate reactor by esterification of more carboxylic acids of formula (III)

(ill) with one or more alcohols R2-OH, wherein said one or more carboxylic acids of formula (III) used in the esterification, or a portion thereof, is obtained in step (A-2) and/or said one or more alcohols R2-OH used in the esterification, or a portion thereof, is obtained in step (A-2).

The term ..esterification" indicates reaction conditions suitable for causing a reaction between carboxylic acid of formula (III) with alcohols R2-OH to give carboxylic acid esters of formula (II).

As mentioned above, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R1 is the very same in the compounds of formula (I), (II) and (III). Similarly, in this specific aspect of the present invention and in all corresponding statements regarding preferred embodiments or features, group R2 is the very same in the compounds of formula (II) and alcohol R2-OH.

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I), and similarly group R2 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in alcohol R2-OH.

The term "in a separate reactor" in the specific aspect of the invention above indicates that the esterification of one or more carboxylic acids of formula (III) with one or more alcohols R2-OH to one or more carboxylic acid esters of formula (II) is not conducted in the same reactor in which the reaction of step (A-2) is conducted, but in a separate reactor. Preferably, the process of the invention comprises as an additional step the step of filtering the mixture resulting in step (A-2), in order to separate solid particles, e.g. humins, from a liquid phase.

It is an achievement of the present invention that in step (A-2) a (co-)solvent for a subse- quent reaction (e.g., oxidation reaction) (B-1 ) is produced. Therefore, typically, no additional solvent or only a mass of solvent, which is smaller than the mass of carboxylic acid of formula (III) present in the mixture after step (A-2) needs to be added between step (A- 2) and subsequent step (B-1 ). Moreover, costly storage units for solvents, more precisely for acidic solvents, for the (oxidation) reaction in subsequent step (B-1 ) are not neces- sary.

In particular, a process according to the present invention as described above or below is preferred, wherein said additional treatment steps comprise

(A-3) separating by distillation from said mixture resulting in step (A-2) at least a portion of the one or more alcohols R2-OH and/or at least a portion of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II).

Preferred is also a process according to the present invention as described herein above or below, wherein said additional treatment steps comprise (A-3-a) separating by distillation from said mixture resulting in step (A-2) at least 50 wt.-%, preferably at least 90 wt.-%, more preferably at least 99 wt.-% of the total weight of said one or more alcohols R2-OH and/or at least 50 wt.-%, preferably at least 90 wt.-%, more preferably at least 99 wt.-% of the total weight of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II). When distilling a portion of the one or more alcohols R2-OH and a portion of the remaining fraction of said amount of one or more carboxylic acid esters of formula (II) from said mixture resulting in step (A-2), the carboxylic acids of formula (III) remain and can be used as the predominant solvent in a subsequent step (B-1 ). They are preferred (co- )solvents for a subsequent oxidation to FDCA and lead to an increased yield in FDCA in an oxidation step (B-1 ).

Due to the intrinsic chemistry of a process of the invention, group R1 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in the carboxylic acids of formula (III) and is present in HMF esters of formula (I), and similarly group R2 as provided in carboxylic acid esters of formula (II) in the resulting mixture of step (A-2) is present in alcohol R2-OH.

In particular, a process according to the present invention as described above or below is preferred, wherein the total yield of 5-(Hydroxymethyl)furfural and 5- (acetoxymethyl)furfural is at least 40 %. Processes with a total yield of 5-(Hydroxymethyl)furfural and 5-(acetoxymethyl)furfural of at least 40 % are of particular industrial relevance and constitute a distinct technical field that is different from other processes that exhibit a total yield of 5-(Hydroxymethyl)furfural and 5-(acetoxymethyl)furfural of less than 40 %, as the latter processes cannot be readily implemented in typical industrial scale full-value-chain-processes resulting in highly processed goods.

Furthermore, a process according to the present invention as described above or below is preferred, wherein the starting mixture prepared or provided in step (A-1 ) does not comprise one or more ionic liquids.

This is due to the fact that the presence of ionic liquids, and to a lesser extent the pres- ence of high boiling solvents (that means solvents with a boiling point >200 °C), is disadvantageous with respect to process efficiency and the time and effort needed for product purification, therefore reducing the applicability of the process in typical industrial scale full-value-chain-processes.

Hereinafter, preferred exemplary processes according to the present invention as de- scribed above or below are disclosed. The advantages of these preferred processes are readily apparent to the skilled person from the detailed description of the invention given above and/or below.

A process according to the present invention as described above or below is preferred, wherein the starting mixture prepared or provided in step (A-1 ) has an acid value below 50, preferably below 5, more preferably below 1 and wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate.

A process according to the present invention as described above or below is preferred, wherein the starting mixture prepared or provided in step (A-1 ) has an acid value below 1 and comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein the total concentration of Br0nsted acids in the starting mixture prepared or provided in step (A-1 ) is lower than 0.15 mol/L, preferably lower than 0.1 mol/L, even more preferably lower than 0.05 mol/L, most preferably 0.01 mol/L and wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate.

A process according to the present invention as described above or below is preferred, wherein the total concentration of Br0nsted acids in the starting mixture prepared or provided in step (A-1 ) is lower than 0.01 mol/L and wherein said starting mixture comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of: LiCI,

LiBr, NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate and wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein said one or at least one of said more carboxylic acid esters of formula (II) is selected from the group consisting of methyl formate, ethyl formate, butyl formate methyl acetate, ethyl acetate, and butyl acetate, preferably selected from the group consisting of methyl acetate, ethyl acetate, and butyl acetate, more preferably methyl acetate and wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two or more catalysts being an alkali halide selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate, wherein the starting mixture prepared or provided in step (A-1 ) has an acid value below 1 and wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate, wherein the total concentration of Br0nsted acids in the starting mixture prepared or provided in step (A-1 ) is lower than 0.01 mol/L and wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

A process according to the present invention as described above or below is preferred, wherein said one or at least one of said more carboxylic acid esters of formula (II) is methyl acetate, wherein the total yield of 5-(Hydroxymethyl)furfural and 5- (acetoxymethyl)furfural is at least 40 %, wherein the total concentration of Br0nsted acids in the starting mixture prepared or provided in step (A-1 ) is lower than 0.01 mol/L and wherein the starting mixture prepared or provided comprises a catalytically effective amount of one, two or more catalysts being an alkali halide, preferably a sodium halide or lithium halide, more preferably selected from the group consisting of:

LiCI,

LiBr,

NaCI and

NaBr.

By using carboxylic acid esters of formula (II) as solvent in step (A-2), carboxylic acids of formula (III) are formed which serve as very good solvent in a subsequent oxidation step (B-1 ). Therefore, no further type of solvent needs to be added reducing the complexity of reactor set-ups compared to processes known in the prior art. Thus, preferably in a process of the present invention (in particular in a process as described above as being preferred) one or more specific carboxylic acids of formula (III) are formed in step (A-2).

The invention also relates to the use of a carboxylic acid ester of formula (II),

O II

R1 c. R2

O

(ii), wherein in each of said carboxylic acid esters of formula (II)

R1 is

(i) hydrogen or a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, and

R2 is a substituted or unsubstituted, branched or linear or cyclic, aliphatic hydrocarbon radical having a total number of 10 carbon atoms or less, in a process for preparing 5-(hydroxymethyl)furfural and HMF esters of formula (I)

(I) wherein R1 is

(i) hydrogen or

(ii) a substituted or unsubstituted, branched or linear, saturated or unsaturated or aromatic hydrocarbon radical having a total number of 21 carbon atoms or less, from carbohydrate compounds as described above, - as the solvent or as a co-solvent for said carbohydrate compounds and

- as dehydration agent.

Generally, all aspects and definitions of the present invention discussed herein above in the context of a process for preparing a mixture comprising HMF or one or more HMF esters of formula (I) according to the present invention apply mutatis mutandis to the use of a carboxylic acid ester of formula (II) according to the present invention. And likewise, all aspects of the inventive use of a carboxylic acid ester of formula (II) discussed herein above or below apply mutatis mutandis to a process for preparing a mixture comprising HMF and one or more HMF esters of formula (I) according to the present invention. As mentioned above, in many industrial cases it is preferred to employ alkyl formates of the formula R2-0-C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is hydrocarbon radical as defined herein above or below (as for alternative (ii), the corresponding carboxylic acid esters of formula (II) are preferred over said alkyl formates of the formula R2-0-C(=0)H.

As HMF is esterified to HMF ester of formula (I) in the overall reaction scheme carboxylic acid esters of formula (II) also act as esterification agents. Therefore, according to the present invention, carboxylic acid esters of formula (II) can also be used as esterification agent for HMF in a process for preparing 5-(hydroxymethyl)furfural and HMF esters of formula (I) and optionally for preparing furan-2,5-dicarboxylic acid.

Preferred is the use of a carboxylic acid ester of formula (II), wherein R1 is

(i) hydrogen (preferred in specific industrial cases) or

(ii) a linear or branched, saturated or unsaturated hydrocarbon radical having 15 carbon atoms or less, more preferably a linear or branched, saturated or unsaturated hydrocarbon radical having 8 carbon atoms or less, even more preferably a linear or branched, aliphatic radical having 6 carbon atoms or less, particularly more preferably -CH ₃ , -CH ₂ CH ₃ , -CH(CH ₃ )CH ₃ , -C(CH ₃ ) ₃ , - CH ₂ CH ₂ CH ₃ , or -CH ₂ CH ₂ CH ₂ CH ₃ , most preferably -CH ₃ , and/or

R2 is a substituted or unsubstituted, branched or linear or cyclic, alkyl radical having a total number of 10 carbon atoms or less, preferably a substituted or unsubstituted, branched or linear or cyclic, alkyl radical having a total number of 6 carbon atoms or less, more preferably a unsubstituted alkyl radical selected from the group consisting of methyl, ethyl, prop-1 -yl, propan-2-yl, butan-1-yl, butan-2-yl, pentan-1 -yl, pentan-2-yl, pentan-3-yl, 2-methylpropan-1-yl, 2-methylpropan-2-yl, 2- methylbutan-1-yl, 3-methylbutan-1-yl, 2-methylbutan-2-yl, 3-methylbutan-2-yl, cyclopentyl, and cyclohexyl, even more preferably methyl.

As mentioned above, in some industrial cases it is preferred to employ alkyl formates of the formula R2-0-C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is hydrocarbon radical as defined herein above or below (as for alternative (ii)), the corresponding specific carboxylic acid esters of formula (II) as described in the specific aspect above are preferred over said alkyl formates of the formula R2-0-C(=0)H. Particularly preferred is the use of a carboxylic acid ester of formula (II), wherein said one or at least one, preferably all, of said more carboxylic acid esters of formula (II) is selected from the group consisting of methyl formate, ethyl formate, butyl formate methyl acetate, ethyl acetate, and butyl acetate, preferably selected from the group consisting of methyl acetate, ethyl acetate, and butyl acetate, more preferably methyl acetate.

As mentioned above, in some industrial cases it is preferred to employ alkyl formates of the formula R2-0-C(=0)H (as for alternative (i), meaning R1 = H) as they are readily available. However, in other cases, where R1 is hydrocarbon radical as defined herein above or below (as for alternative (ii), the corresponding specific carboxylic acid esters of formula (II) as defined in the specific aspect above are preferred over said alkyl formates of the formula R2-0-C(=0)H. Hereinafter, the invention will be explained in some more detail with reference to the attached drawings.

Figures:

Fig. 1 :

Fig. 1 is a schematic drawing of typical reactions taking place in an exemplary process of the present invention.

In Fig. 1 the term "fructose/glucose" is used to designate an example of said "one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units" present in the starting mixture prepared or provided in process step (A-1 ).

"MeOAc" indicates methyl acetate and correspondingly designate an example of said "one or more carboxylic acid esters of formula (II)" as present in the starting mixture prepared or provided in step (A-1 ).

According to the first reaction depicted in Fig. 1 , fructose/glucose is subjected to reaction conditions so that HMF is formed. MeOAc is the solvent for fructose/glucose according to the first reaction of Fig. 1. Three equivalents of water are produced when fructose/glucose is transformed into HMF.

According to the second reaction depicted in Fig. 1 , MeOAc reacts with water (e.g. water as produced by the reaction of fructose/glucose to HMF) and as a result acetic acid as well as methanol (MeOH) is formed.

According to the third reaction depicted in Fig. 1 HMF reacts with acetic acid (AcOH) to give the corresponding HMF ester (acetylated HMF; i.e., an HMF ester of formula (I) with

R1 = CH ₃₎ .

Summarizing, fructose/glucose and MeOAc (which acts both as a solvent and a reaction partner) react to give acetylated HMF (as an example of an HMF ester of formula (I)) as well as methanol (as an example of an alcohol R2-OH) and acetic acid (AcOH; an example of a carboxylic acid of formula (III)). Furthermore produced are three equivalents of water. As HMF produced by dehydration of fructose/glucose is typically not reacted quantitatively with acetic acid in a typical scenario the reaction product mixture also comprises HMF.

Fructose/glucose as well as MeOAc are considered to be compounds of the starting mixture prepared or provided in step (A-1 ) of the present invention. HMF, the HMF ester (acetylated HMF), acetic acid and methanol as well as a remaining fraction of MeOAc are considered as components of the mixture resulting in process step (A-2). In schematic Fig. 1 MeOAc is not depicted on the right hand side of any of the reactions shown, as the major amount of MeOAc is reacted.

Fig. 2: Fig. 2 is a schematic drawing of typical (exemplary) process steps conducted in a process of the present invention, where in subsequent steps FDCA is produced.

In Fig. 2, the term "sugar" is used to indicate an example of said "one, two or more carbohydrate compounds selected from the group consisting of hexoses, oligosaccharides comprising hexose units, and polysaccharides comprising hexose units" present in the starting mixture prepared or provided in process step (A-1 ).

The sugar is first dehydrated in a dehydration reactor which is co-fed with MeOAc (methyl acetate (as an example of a carboxylic acid ester of formula (II)). In the dehydration reactor, a mixture results comprising HMF and/or 5-(acetoxymethyl)furfural (AMF, as an example of a HMF ester of formula (I)), methanol (as an example of an alcohol R2-OH), acetic acid (as an example of a carboxylic acid of formula (III)) and a remaining fraction of methyl acetate.

The resulting mixture (corresponding to a mixture resulting in step (A-2) according to the present invention) is subsequently distilled in order to remove methyl acetate and methanol. After separating methanol and methyl acetate from the mixture comprising the remaining compounds

(i) acetic acid, and

(ii) HMF and/or AMF, to said mixture,

(iii) more acetic acid can optionally be added if needed (not shown in Fig. 2).

Subsequently said mixture comprising (i) acetic acid, and (ii) HMF and/or AMF and (iii) optionally additional acetic acid is subsequently subjected to oxidation conditions (according to step (B-1 )) in order to give a product mixture comprising FDCA and acetic acid.

In a final purification step, the FDCA is separated from the acetic acid remaining after the subsequent oxidation reaction in step (B-1 ).

The separated acetic acid is subsequently esterified to methyl acetate by reaction with the methanol, which has been separated together with methyl acetate in the distillation step prior to the oxidation. In said esterification step, water is formed as a co-product, and disposed. A resulting mixture mainly comprises methyl acetate and is recycled into the dehydration reactor.

Thus, in the overall process scheme in Fig. 2, sugars are converted into purified FDCA with water being the only relevant by-product produced in the overall process in significant amounts.

Hereinbelow, the invention is described in more detail by examples: Examples:

Quantification method: Quantification by GC:

The quantification of products has been done by GC-analysis with a Agilent Technologies 6890N GC with 7693 Autosampler and a 5973 MSD (Column: VF624ms with dimensions of 60ιη ^* 0,25ιηιη ^* 1 ,4μιη. The different GC set-up parameters have been: injection volume: 1 μΙ_. Inlet: 200°C, Split: 60: 1 , Flow: 0,8ml/min constant flow. Oven: start temp: 50 °C; 3°C/min to 300°C hold for 7 minutes)

Experiments 1 to 24: Reaction parameter screening Experimental procedure of screening experiments 1 to 24:

Screening was carried out in a series of single experiments designated "Experiment 1 " to "Experiment 24".

In each single experiment "1 " to "24", one or more carbohydrate compounds according to the present invention was at least partially converted into HMF and 5- (acetoxymethyl)furfural (as an example of a carboxylic acid ester of formula (I) according to the present invention) in methyl acetate (MeOAc, solvent used as an example of a carboxylic acid ester of formula (II) according to the present invention).

The general experimental procedure for each screening experiment of "1 " to "24" was as follows: In a first step (as an example of step (A-1 ) of a process according to the invention), a starting mixture was prepared by filling

- 60 g of methyl acetate,

- a specific amount of fructose (see experiments 1 to 12 in table 1 and experiments 21 to 24 in table 3 below) or an agueous fructose syrup with at least 66.5 wt-% fructose and some glucose (see experiments 13 to 20 in table 2 below). and

- a catalyst (also designated as "additive", only for experiments 9 to 13 and 15 to 20) into a steel autoclave reactor (inner volume 300 ml). The amounts of fructose or fructose syrup were in the range of from: Fructose: 3.0-12.0 g (see table 1 below);

Fructose syrup: 6.0-38.0 g (see table 2 below).

In a second step (as an example of step (A-2) of a process according to the invention), the filled steel autoclave reactor was tightly sealed and pressurized with nitrogen (total pressure 50 bar) and the reaction mixture inside the steel autoclave reactor was heated to a temperature of 100-240°C (see table 1 , 2 and 3 below) while stirring at 1000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 1-40 hours (see table 1 , 2 and 3 below) while continuing stirring the reaction mixture inside the heated and pressurized steel autoclave reactor.

Subsequently, the steel autoclave reactor was

(i) allowed to cool down to room temperature (approximately 22 °C),

(ii) the pressure was released, and

(iii) the steel autoclave reactor was opened.

For further analysis, 1 mL of the resulting mixture comprising HMF, 5- (acetoxymethyl)furfural, acetic acid, methanol and a remaining fraction of the initially added 60 g of the MeOAc was subjected to GC analysis to quantify said reaction products.

Yield:

HMF yield [%] = n _HMF / Π Fructose

AMF yield [%] = n _AMF / ΓΊ Fructose

Di-HMF yield [%] = (n _Di _ _H M _F x 2) / n _Fmctose Furfural yield [%] = n _Furfura |/ n _FructoS e overall yield [%] = HMF yield [%] + AMF yield [%] + Di-HMF yield [%]

If not indicated otherwise, molar amounts and the corresponding yields are calculated on the basis of GC data.

Experimental results of the screening experiments described above (1-23) according to the present invention:

In table 1 and 2, the reaction time, the reaction temperature, the type and amount of catalyst used, the initial amount of fructose (table 1 ) or the initial amount of fructose syrup (table 2), respectively, the HMF yield, AMF yield, di-HMF yield, furfural yield and the overall (total) yield of each single experiment of the screening experiments 1 to 23 described above are shown.

Exp. T time type FrucHMF AMF Di-HMF Furfural over¬

[°C] [ ] of tose yield yield yield yield all cata[g] [%] [%] [%] [%] yield lyst / [%] correspond

ing

weight

[g]

1 200 2 - 3 7.9 0.6 1.0 1 .8 26.4

2 200 5 - 3 6.9 2.4 1.2 1 .9 27.5

3 200 5 - 6 1 1.4 12.7 2.6 4.1 35.3

4 200 5 - 12 19.6 18.7 2.4 8.6 40.6

5 180 16 - 12 12.2 20.7 2.0 5.6 34.9

6 180 16 - 6 18.1 19.6 1.6 5.6 39.4

7 160 16 - 6 20.7 1.9 0.6 1.2 34.4

8 140 16 - 6 12.2 0.1 0.1 0.5 19.3 9 LiCI/

200 16 3 10.3 29.9 0.4 1.8 40.5

0.023

10 LiCI/

220 2 12 21.9 23.2 0.8 1.5 45.9

0.141

11 NaCI/

220 2 12 23.9 23.0 0.8 1.8 47.7

0.195

12 FeCI ₃ /

200 16 3 0.6 2.4 0.2 8.6 3.2

0.135

Table 1 : Experimental parameters and yield of catalyst screening experiments with

(i) fructose as carbohydrate compound of the present invention and

(ii) 60 g of MeOAc as a carboxylic acid ester of the present invention.

When comparing the overall (total) yield of Experiments 1 to 8 with Experiments 9 to 12, it can be seen that reactions with LiCI or NaCI as a catalyst have an increased overall yield. Thus, using LiCI or NaCI as a catalyst is preferred.

A comparison between Experiments 1 and 2 shows that more AMF is produced when the duration of the reaction is increased. Thus, a longer duration of the reaction is preferred to yield more AMF.

When changing the initial amount of fructose from 3 to 12 g at constant reaction time and constant reaction temperature, the overall yield is increased (see experiments 2 to 4). Thus an amount of fructose in the starting mixture up to 20 wt.-% is preferred in order to increase the overall yield. In experiments 6 to 8, the reaction temperature is decreased from 180 °C to 140 °C while the remaining parameters are kept constant. As a consequence, the AMF yield is increased up to 19.9 % (at 180 °C). As a result, the ratio of HMF to AMF is decreased with increasing reaction temperature. Thus, high reaction temperatures are preferred.

In experiments 9 to 12, three different catalysts were added to the starting mixture. The overall yield was increased when LiCI and NaCI (experiments 10 and 1 1 ) were used as a catalyst but decreased when FeCI ₃ was used instead (experiment 10 vs. 13). Thus, alkali halides are preferred over other metal halides. Exp. T time NaCI FrucHMF AMF Di-HMF Furfural overall

[°C] [ ] [g] tose yield yield yield yield yield syrup [%] [%] [%] [%] [%]

[g]

13 220 2 0.19 12 41.2 22.4 0.4 1.7 64.1

14 220 2 - 12 24.3 18.2 1.2 9.9 43.7

15 200 1 0.19 12 38.4 1 1.6 0.4 1.1 50.4

16 200 2 0.19 12 37.9 19.0 0.2 1.3 57.1

17 200 4 0.19 12 36.8 22.4 0.2 1.2 59.4

18 200 4 0.39 6 19.3 19.4 0.2 1 1 .9 38.9

19 200 4 0.19 24 29.9 10.7 0.4 1.1 41.0

20 200 4 0.19 36 24.5 6.3 0.4 1.1 31.2

Table 2: Experimental parameters and yield of catalyst screening experiments with

(i) fructose syrup as carbohydrate compounds of the present invention and

(ii) 60 g of MeOAc as a carboxylic acid ester of the present invention.

Comparing the overall yield of experiment 13 (with NaCI as catalyst) to the overall yield of experiment 14 (without catalyst), a significant increase in the overall yield and in the selectivities was observed.

In experiments 15 to 17, the reaction time is changed from 1 h to 4h at a constant initial concentration of fructose of 7.9 g and a constant reaction temperature of 200 °C. An increase in the overall yield from 50.2 % to 59.3 % was measured with increasing reaction time. Thus, a longer duration of the reaction is preferred when using a catalyst.

In experiments 17 to 20, the initial concentration of fructose is changed from 3.7 to 32.3 g at a constant reaction time of 4 h and a constant reaction temperature of 200 °C. The overall yield is increased to 59.3 % when using 7.9 instead of 3.7. However, when increasing the initial concentration of fructose further to 32.3 g the overall yield decreases to 31.0 %. Thus, the amount of fructose in the starting mixture in step (A-1 ) is preferably between 10 and 20 wt.-%.

Experiments 21 to 24: Specific effect of reaction time and reaction temperature In order to see the effect of the reaction time and reaction temperature in the dehydration step of the carbohydrate compounds (as in step (A-2) of the invention) on the molar ratio of HMF / AMF in a resulting mixture, experiments 21 to 24 have been conducted at different temperatures and/or different reaction times (see table 3).

Table 3: Effect of reaction time and reaction temperature in catalyst screening experiments 23 to 26 with

(i) fructose as carbohydrate compounds of the present invention

and

(ii) 60 g of MeOAc as a carboxylic acid ester of the present invention.

The results of experiments 21 to 24 show that the molar ratio HMF/AMF can be adjusted by selecting reaction time and reaction temperature, when using otherwise identical reaction conditions. When using temperatures of 200 °C and 240 °C, respectively, the molar ratio HMF/AMF is significantly lower than at a reaction temperature of 160 °C (see Experiments 1 , 3, 4 versus Experiment 2). A comparison of Experiments 1 and 3 shows that at the identical temperature of 200 °C, the molar ratio HMF/AMF decreases when the duration of the reaction is increased. Thus, in order to arrive at a low molar ratio HMF/ AMF it is preferred to employ a reaction temperature in the range of from 160 to 240 °C.