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Crystallization of Furanic Compounds

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Crystallization of Furanic Compounds (19) TZZ¥Z_¥_T (11) EP 3 015 463 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 04.05.2016 Bulletin 2016/18 C07D 307/48 (2006.01) (21) Application number: 14191075.2 (22) Date of filing: 30.10.2014 (84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • URBANUS, Jan, Harm GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO 2595 DA ’s-Gravenhage (NL) PL PT RO RS SE SI SK SM TR • VERDOES, Dirk Designated Extension States: 2595 DA ’s-Gravenhage (NL) BA ME • ROA ENGEL, Carol Andrea 2595 DA ’s-Gravenhage (NL) (71) Applicant: Nederlandse Organisatie voor toegepast- (74) Representative: V.O. natuurwetenschappelijk onderzoek TNO P.O. Box 87930 2595 DA ’s-Gravenhage (NL) 2508 DH Den Haag (NL) (54) Crystallization of furanic compounds (57) The invention relates to a method for preparing - preferably removing water from the product mixture; and furanic compound crystals from sugars comprising the - simultaneously crystallizing the furanic compound and steps of the organic solvent by cooling the product mixture, there- - converting sugar or sugar alcohol into a furanic com- by obtaining a slurry comprising solvent crystals and fu- pound in a reaction mixture comprising an organic sol- ranic compound crystals; and vent, thereby obtaining a product mixture comprising a - separating the solvent crystals and the furanic com- furanic compound dissolved in said organic solvent and pound crystals. water; EP 3 015 463 A1 Printed by Jouve, 75001 PARIS (FR) 1 EP 3 015 463 A1 2 Description niques have resulted in other problems. The processes are energy consuming, produce additional waste (e.g. [0001] The invention is directed to a method for pre- due to additional organic solvent use) and/or require ex- paring furanic compounds and a mixture of furanic com- pensive equipment. Further, they can often not be easily pound crystals and organic solvent crystals obtained5 implemented at full industrial scale at acceptable energy therein. and investment costs. [0002] Furanic compounds, such as furfural (FF) and [0008] Accordingly, there is still a need for alternative hydroxymethylfurfural (HMF), are nowadays becoming methods for preparing and processing HMF. In particular, more and more important as renewable building blocks there is a need for a process wherein HMF and the or- for chemical industry. Furanic compounds are typically 10 ganic solvent in which it is prepared can be efficiently produced from sugars. For example, HMF can be pre- separated, while the process can at the same time be pared by the conversion of fructose into HMF. Furfural implemented at full industrial scale at acceptable energy has been produced from sugars on a commercial scale and investment costs. for several decades, while efforts are recently made to [0009] It is therefore an object of the invention to pro- also scale-up HMF production. 15 vide a process for preparing furanic compounds from [0003] The current commercial process with which fu- sugar in an organic solvent, wherein the furanic com- ranic compounds are produced is by sugar conversion pound can be efficiently separated from the reaction mix- in an aqueous media, which resulted in a yield of 50-60%. ture. More in particular, an object of the invention is to However, it has recently been found that furanic com- achieve this by a relatively simple and energy efficient pounds can also be produced in an organic solution. An 20 process that can easily be scaled up to industrial scale. advantage of producing furanic compounds from sugars [0010] This object was met by providing a method for in an organic solvent instead of in water is that less by- preparing furanic compound crystals from sugars com- products is formed and that a higher yield can be ob- prising the steps of tained, typically over 90%. The organic solvent used in convertingsugar into furaniccompounds must be aprotic. 25 - converting sugar or sugar alcohol into a furanic com- This facilitates solubilization of the sugar feedstock and pound in a reaction mixture comprising an organic further to enable the conversion into furans (in particular solvent, thereby obtaining a product mixture com- when the conversion is acid-catalyzed). prising a furanic compound dissolved in said organic [0004] Although conversion in an organic solution has solvent and water; been studied at small scale, furanic compounds have not 30 - optionally further converting the furanic compound; yet been successfully produced at commercial scale. To and achieve this, a number of problems still need to be solved. - preferably removing water from the product mixture; [0005] One problem of sugar conversion to furanic and compounds in an organic solvent is the separation of the - simultaneouslycrystallizing the (convertedor uncon- furanic compound from the organic solvent. The organic 35 verted) furanic compound and the organic solvent solvents are known to interact with furanic compounds by cooling the product mixture, thereby obtaining a such that separation is difficult. slurry comprising solvent crystals and furanic com- [0006] In the past years, several techniques have been pound crystals; and tested to solve this problem. - separating the solvent crystals and the furanic com- [0007] For example, FR 2 669 635 describes a process 40 pound crystals. for preparing HMF in an aprotic solvent, after which water and a second organic solvent are added to extract the [0011] The inventors found that simultaneous crystal- HMF formed. Thus, two liquid phases are formed, which lization of the product and the solvent resulted in a very are separated. HMF is crystallized by cooling the second efficient separation To the inventors’ knowledge, simul- liquid phase. WO 2013/024162 describes a procedure 45 taneous crystallization by cooling (also known as eutectic for purifying HMF by crystallization at low temperature freeze crystallization) has never been considered before from an organic solvent having a freezing point of -50°C as a viable separation technique in the field of furanic or lower by cooling the solution to a temperature of be- compound synthesis. Up to now, eutectic freeze crystal- tween 0 and -40°C. Precipitated solid HMF is isolated by lization has only been used for removal of salt and/or filtering the obtained suspension. Given the nature of 50 organic contaminants from aqueous streams, for exam- most solvents with the specified melting point, this pro- ple in waste water treatment. The inventors found that cedure typically applies to the process described by FR this technique could also be applied for isolation and sep- 2 669 635, where a solvent is added to the aprotic solvent aration of furanic compounds from an organic solvent in which the reaction takes place. Although these and after sugar conversion. The efficient separation of the other separation techniques of the prior art, such as dis- 55 furanic compound and the organic solvent is also illus- tillation, membrane assisted pervaporation, extraction in- trated in the Examples. to other solvents, adsorption and chromatography, have [0012] The inventors further realized that it is not de- been proven to effectively isolate the HMF, these tech- sirable to directly subject the product mixture obtained in 2 3 EP 3 015 463 A1 4 the conversion step to simultaneous crystallization. In to the specific temperature (referred to as the "eutectic such a case, complications would arise during crystalli- temperature") and the specific ratio between the organic zation and/or separation of the product and solvent. For solvent and furanic compound (referred to as the "eutec- example, a mixture of three solids may be formed, which tic composition" or "eutectic ratio") in the product mixture considerably complicates the separation step. The inven- 5 at which simultaneous crystallization of the organic sol- tors realized that such complications were caused by the vent and the furanic compound occurs. Although the presence of water in the product mixture. Water is formed product mixture may have more than one eutectic point as a byproduct during the conversion of sugar into furanic (e.g. due to the presence of other components in the compounds and is therefore necessarily present in the mixture, such as byproducts or reactants of the first product mixture obtained in the conversion step. By re- 10 and/or second conversion reaction), the eutectic point as moving water from the product mixture prior to simulta- referred to in the present invention only concerns the neous crystallization, the afore-mentioned complications eutectic point at which the organic solvent and the furanic can thus be avoided. Thus, a particular efficient crystal- compound simultaneously crystallize. lization and/or separation is achieved. [0020] The different steps of the method of the inven- [0013] Further, it was found that by selecting a suitable 15 tion will be discussed in more detail below. combination of a furanic compound and an organic sol- [0021] In the first step, sugar is converted into a furanic vent, the temperature at which crystallization occurs can compound in a reaction mixture comprising an organic be controlled. As such, a crystallization temperature may solvent. This step may also be referred to as the sugar be used in the process ( e.g. just below 20 °C), such that conversion or first conversion step. The reaction mixture the energy consumption for cooling will be small. Thus, 20 may further comprise a catalyst to promote the conver- the process of the invention provides for an energy effi- sion of the sugar into the furanic compound and/or to cient separation process. Further, since the method only promote the further conversion of the furanic compound requires relatively simple crystallization and cooling if such a step is conducted. The catalyst may be in solid equipment, the method can be suitably scaled up to in- form (in case of heterogeneous catalysis) or in dissolved dustrial scale without the need of expensive equipment.
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