EP2791127A1 - Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau - Google Patents

Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau

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Publication number
EP2791127A1
EP2791127A1 EP12809657.5A EP12809657A EP2791127A1 EP 2791127 A1 EP2791127 A1 EP 2791127A1 EP 12809657 A EP12809657 A EP 12809657A EP 2791127 A1 EP2791127 A1 EP 2791127A1
Authority
EP
European Patent Office
Prior art keywords
hmf
solution
starting
starting solution
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12809657.5A
Other languages
German (de)
English (en)
Inventor
Ralf Böhling
Benoit BLANK
Alois Kindler
Carmen FELDNER
Sandra UMLAUF
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
BASF SE
Original Assignee
BASF Schweiz AG
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Schweiz AG, BASF SE filed Critical BASF Schweiz AG
Priority to EP12809657.5A priority Critical patent/EP2791127A1/fr
Publication of EP2791127A1 publication Critical patent/EP2791127A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

Definitions

  • the present invention relates to a process for the preparation of solutions containing 5-hydroxymethylfurfural (HMF) and having a reduced content of starting materials of HMF synthesis or a reduced content of by-products of HMF synthesis (hereinafter referred to as product solution), which characterized in that solutions which
  • An organic solvent containing at least two ether groups (polyether short) (hereinafter referred to as starting solution), are treated in an evaporator with steam.
  • HMF 5-hydroxymethylfurfural
  • 2,5-furandicarboxylic acid which is suitable as a dicarboxylic acid for the preparation of polymers such as polyesters or polyurethanes, and can replace other dicarboxylic acids from non-renewable raw materials in industrial applications.
  • HMF is typically produced by acid catalyzed dehydration of hexoses such as glucose or fructose.
  • reaction product acidic solutions are obtained, which in addition to the HMF unreacted starting materials and / or by-products.
  • HMF synthesis is usually only a partial conversion of the starting materials in order to avoid the formation of by-products.
  • the resulting solutions contain unreacted starting materials such as hexoses or oligomers or polymers made up of hexoses. With higher sales, the amount of by-products increases.
  • HMF is named after Mark Mascal and Edward B. Nikitin in 2008 Angew. Chemie Vol. 47, pages 7924-7926 converted into the more stable 5-chloromethyl furfural and then converted back into HMF or its derivatives.
  • the ethers or, according to EP-A 1834951, the esters of HMF are prepared which, after separation, are directly suitable for further syntheses.
  • HMF should be in as pure as possible form for further syntheses.
  • aqueous solution of HMF are suitable, which by-products or residual starting materials not or at most in very small amounts.
  • Previously known methods to produce HMF or its aqueous solutions with sufficient purity are extremely expensive.
  • the object of the present invention was therefore a process by means of which HMF or its aqueous solutions can be made available in as simple and effective a manner as possible in the purest possible form.
  • HMF-containing starting solutions are subjected to a steam distillation in order to obtain HMF-containing product solutions having a reduced content of starting materials or by-products from the synthesis.
  • Starting solutions are preferably solutions obtained in the production of HMF.
  • HMF is usually prepared by acid-catalyzed dehydration of hexoses, for example glucose or, in particular, fructose.
  • the hexoses may in turn be obtained from oligomeric or polymeric compounds such as starch, cellulose in advance or in situ when dehydration is carried out.
  • the reaction can produce by-products.
  • the dehydration is preferably carried out in aqueous solution, but in principle other solvents or mixtures of solvents can also be used.
  • the solutions obtained in the dehydration can therefore various compounds, such as unreacted starting materials (hexoses, starch, celluloses), acid used as catalyst (short acid catalyst), solvents or by-products of HMF synthesis (carboxylic acids, HMF oligomers, Humines).
  • the solutions obtained in the dehydration can, if desired, be worked up before use as starting solution, eg.
  • the solutions may be filtered to separate solids.
  • the solutions obtained may already be free of acid. The latter is z.
  • Example the case when heterogeneous acids were used, which can be easily separated as a solid or which were introduced in the reaction in a fixed bed and therefore do not get into the reaction solution.
  • the starting solution contains
  • the starting solution usually contains HMF in amounts of from 1 to 30% by weight, more preferably from 2 to 20% by weight, based on the total weight of the starting solution.
  • the starting solution may contain starting materials of HMF synthesis.
  • the starting materials of the HMF synthesis are hexoses or oligomers or polymers made up of hexoses (hereinafter referred to collectively as saccharides).
  • the starting solution may therefore contain, in particular, hexoses, oligomers or polymers composed of hexoses or polymers or both hexoses and oligomers or polymers made therefrom.
  • Preferred hexoses are fructose or glucose, in particular fructose or mixtures of fructose and glucose.
  • Oligomers or polymers of the hexoses are preferably starch or cellulose.
  • the content of the starting solution of total saccharides in a particular embodiment is more than 0.1% by weight, in particular more than 0.5% by weight, preferably more than 1% by weight, based on the total weight of the starting solution.
  • the content of the starting solution of total saccharides is generally not more than 20% by weight, in particular not more than 10% by weight, based on the total weight of the starting solution.
  • At least 50% by weight, in particular at least 70% by weight, of the saccharides present in the starting solution are hexoses, e.g. fructose or glucose, preferably fructose or mixtures of fructose and glucose with a proportion of more than 50% by weight of fructose.
  • hexoses e.g. fructose or glucose, preferably fructose or mixtures of fructose and glucose with a proportion of more than 50% by weight of fructose.
  • the starting solution may contain by-products of HMF synthesis.
  • By-products whose content is reduced by the process according to the invention are in particular HMF oligomers (so-called humins).
  • the content of humins in the starting solution can, for. B. 0 to 10 wt.%, In particular 0 to 5 wt.% Be.
  • the starting solution contains at least 0.05% by weight, in particular at least 0.1% by weight of humins.
  • carboxylic acids in particular formic acid, acetic acid, levulinic acid or mixtures thereof.
  • the starting solution may further contain acids which have been used as catalyst in the preparation of the HMF.
  • the acids dissolved in the starting solution are (homogeneous acids).
  • Heterogeneous acids (solids), which were used as catalysts in the preparation of the HMF, can easily be separated in advance or even not get into the starting solution, as already described above.
  • Suitable (homogeneous) acids are any inorganic or organic acids. Examples include para-toluenesulfonic acid, methanesulfonic acid (MeOSOßH), oxalic acid, sulfuric acid, hydrochloric acid or phosphoric acid.
  • MeOSOßH methanesulfonic acid
  • oxalic acid sulfuric acid, hydrochloric acid or phosphoric acid.
  • the content of all acids in the starting solution may be, for example, 0 to 10% by weight, based on the total weight of the starting solution.
  • the starting solution contains, as stated above, starting materials or by-products of HMF synthesis.
  • the starting solution may contain starting materials but no by-products of HMF synthesis; this may be the case with partial conversion HMF synthesis.
  • the starting solution may contain by-products of HMF synthesis but no starting materials; this may be the case with full conversion HMF synthesis, but with by-products in larger quantities.
  • the starting solution will contain both starting materials and by-products of HMF synthesis; In particular, it contains both saccharides and humins, preferably in the respective amounts described above.
  • the starting solution contains an organic solvent having at least two ether groups (polyether for short).
  • the polyether can be added to the starting solution, for example shortly before carrying out the process according to the invention; but it may also have been used in the solution in the production of the HMF as a solvent and therefore already be included in the starting solution.
  • the polyether preferably has a boiling point greater than 250 ° C (atmospheric pressure, 1 bar).
  • the polyether preferably has a melting point of less than 60 ° C, in particular less than 30 ° C (at atmospheric pressure, 1 bar); more preferably, the polyether at 20 ° C (atmospheric pressure) is liquid.
  • the polyether preferably contains at least 3, in particular at least 4, more preferably at least 6 ether groups. In general, it contains not more than 40, in particular not more than 30, ether groups, more preferably not more than 20 ether groups.
  • the polyether contains no heteroatoms except oxygen in the form of ether groups and optionally hydroxyl groups.
  • it is an aliphatic polyether, more preferably is a polyalkylene glycol, wherein the terminal hydroxyl groups can be etherified with alkyl groups, especially C1 to C4 alkyl groups.
  • the alkylene groups of the polyalkylene glycols may be e.g. C 2 to C 10, in particular C2 to C4 alkylene groups, such as ethylene, propylene or butylene act.
  • the polyethers may also contain various alkylene groups, e.g. in the form of blocks.
  • poly-C 2 -C 4 -alkylene glycols in particular polyethylene glycol, whose terminal hydroxyl groups may optionally be etherified with alkyl groups; the number of recurring Alkylenether phenomenon corresponds to the above number of ether groups, in particular the number of recurring Alkylenether phenomenon 4 to 30, more preferably 6 to 20.
  • the terminal hydroxyl groups of the polyether may be etherified with alkyl groups, especially C1-C4 alkyl groups.
  • the starting solution preferably contains the polyether in amounts of from 5 to 90% by weight, in particular from 30 to 80% by weight, particularly preferably from 50 to 70% by weight.
  • the starting solution is preferably an aqueous solution since the preparation of HMF is preferably carried out in water.
  • the preparation of HMF is also possible in organic solvents, so that the starting solution may optionally also contain such organic solvents.
  • organic solvents are, for example, polar aprotic solvents such as DMSO, MIBK, MEK, 2-MeTHF and protic solvents, in particular alcohols, ethers, polyethers or polyalkylene glycols (see above).
  • the content of the starting solution of other organic solvents than polyethers (or polyalkylene glycols) is preferably less than 20% by weight, in particular less than 10% by weight and particularly preferably less than 5% by weight.
  • Preferred starting solutions contain z. B.
  • the treatment of the starting solution with steam is preferably carried out at reduced pressure, in particular a pressure of 1 to 300 mbar is considered.
  • the pressure in the evaporator is 1 to 100 mbar, particularly preferably 1 to 50 mbar and in a very particularly preferred embodiment 1 to 40 or 1 to 35 mbar.
  • the treatment of the starting solution with steam is preferably carried out at a temperature of the starting solution of 100 to 200 ° C, particularly preferably from 120 to 180 ° C and more preferably from 140 to 180 ° C and most preferably 150 to 180 ° C. ,
  • the process according to the invention is preferably operated continuously.
  • the starting solution and the steam are fed continuously to the evaporator and the product solution is continuously removed.
  • the volume flows depend on the evaporator size and separation efficiency of the selected evaporator type.
  • Suitable evaporators are customary evaporators, which are set up for the feed of starting solution and steam, and in particular for the continuous procedure described above.
  • Preferred evaporators are thin-film evaporators. In which the starting solution is present in the evaporator as a liquid film.
  • Such vertical thin-film evaporators are known under device designations such as “Luwa” or in particular "Sambay”.
  • the preferred vertical thin-film evaporators are ultimately a vertical tube with internal devices for distribution and mixing of the exit solution and external devices for heating the tube wall.
  • the starting solution is preferably supplied in the upper part of the thin film evaporator and distributed as a film on the heated tube wall.
  • Water vapor can be supplied to the evaporator, preferably to the thin-film evaporator, together with the starting solution or at any other point in the evaporator.
  • the starting solution and the water vapor can be conducted in the same direction (DC) or in the opposite direction (countercurrent) in the evaporator.
  • the water vapor is passed in countercurrent to the starting solution.
  • the starting solution is supplied in particular in the upper part of the evaporator and the steam in the lower part of the evaporator.
  • the water vapor and the volatile constituents of the starting solution are preferably carried out via a separator at the top of the evaporator and condensed (product solution).
  • the non-volatile constituents pass through the evaporator and are separated off as a liquid bottom product.
  • Figure 1 shows a corresponding apparatus of thin-film evaporator (Sambay) and apparatus for condensation.
  • the product solution obtained after condensation contains the HMF separated from the starting solution. It is an advantage of the process according to the invention that HMF can be separated from the starting solution simply, effectively and in large quantities.
  • the product solution contains more than 70%, particularly preferably more than 85%, particularly preferably more than 95%, of the HMF which has been fed to the evaporator via the starting solution.
  • the resulting product solution has a high purity.
  • the content of the product solution of polyether is in particular less than 5% by weight, preferably less than 2% by weight and more preferably less than 1 or less than 0.5% by weight, based on the total weight of the product solution.
  • the content of saccharides in the product solution compared to the content of the saccharides in the starting solution is greatly reduced, or are saccharides in the product solution not or barely contained.
  • the percentage content of all saccharides in the product solution is less than 20% in total, in particular less than 10% of the content of all saccharides in the starting solution.
  • the product solution preferably contains less than 5% by weight, in particular less than 2% by weight, more preferably less than 1% by weight, very preferably less than 0.5% by weight of saccharides, and in a particular embodiment less than 0.1% by weight of saccharides based on the total weight of the product solution.
  • the content of humins in the product solution compared to the content of humins in the starting solution is greatly reduced, or humins are not or barely contained in the product solution.
  • the total content of all humins in the product solution is less than 20%, in particular less than 10%, of the content of humins in the starting solution.
  • the product solution contains less than 5% by weight, in particular less than 2% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight of humins, and in a particular embodiment less as 0.1% by weight of humins, based on the total weight of the product solution.
  • product solutions are obtained in which saccharides and humins are not or hardly detectable and their total content is below 0.5, in particular below 0.1 or below 0.05 wt.%.
  • starting solutions are dark in their content of humins, or black, while the resulting product solutions are clear and bright.
  • the product solution is suitable for chemical syntheses where HMF is used as starting material.
  • the product solution is suitable for chemical syntheses in which the starting material HMF is desired or required in high purity.
  • the use of the product solution for the production of 2,5-furandicarboxylic acid or of 2,5-bis (hydroxymethyl) furan may be mentioned here.
  • Example 1 Synthetic mixtures without sugar Starting solution The starting solution was obtained by mixing pure substances.
  • PEG-400 a polyethylene glycol having a molecular weight of 400
  • PEG-600 a polyethylene glycol with a molecular weight of 600
  • Tetraglyme tetraethylene glycol dimethyl ether
  • the steam distillation was carried out in the apparatus according to FIG.
  • the apparatus consists of a Glassambay, which is operated in Martinezstromfahrweise.
  • the starting solution was fed to the head, the water vapor in the lower third.
  • composition of the product solution for various high boilers and the selected temperatures and pressures are listed in the table.
  • the indicated temperature is that of the heating medium on the tube outer wall, which corresponds to a good approximation to that of the liquid film of the starting solution on the tube inner wall.
  • the composition was determined by HPLC.
  • Table 1 Table 1 :
  • the starting solution was obtained by mixing pure substances.
  • distillate product solution
  • concentrations of distillate and sump do not add to the concentration of the starting solution.
  • the starting solution was obtained by reaction of fructose in a water / high-boiling mixture with p-toluenesulfonic acid as catalyst at 160 ° C.
  • the HMF yield given in the table refers to the HMF contained in the starting solution.
  • the sum of the HMF yield in the distillate and bottom does not always give 100%, since HMF from the starting solution can polymerize to a small extent to humins, whereby the yields are less than 100%. If fructose is still present, small quantities of additional HMF may be produced, which may increase the yields by more than 100%.
  • the starting solution was blackened due to the content of humins.
  • the resulting product solution was clear with a very slight yellowish tint.
  • the product solution was therefore essentially free of humins.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Furan Compounds (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

L'invention concerne un procédé de production de solutions qui contiennent du 5-hydroxyméthylfurfural (HMF) et ont une teneur réduite en substances de départ de la synthèse de HFM ou une teneur réduite en produits annexes de la synthèse de HMF (dénommée ci-après solution de produit). Le procédé est caractérisé en ce que des solutions qui contiennent des substances de départ ou des produits annexes HMF de la synthèse de HMF et un solvant organique comprenant au moins deux groupes éther (en bref polyéther) (dénommée ci-après solution de départ) sont traitées dans un évaporateur avec de la vapeur d'eau.
EP12809657.5A 2011-12-13 2012-12-07 Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau Withdrawn EP2791127A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12809657.5A EP2791127A1 (fr) 2011-12-13 2012-12-07 Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11193154 2011-12-13
EP12809657.5A EP2791127A1 (fr) 2011-12-13 2012-12-07 Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau
PCT/EP2012/074737 WO2013087523A1 (fr) 2011-12-13 2012-12-07 Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau

Publications (1)

Publication Number Publication Date
EP2791127A1 true EP2791127A1 (fr) 2014-10-22

Family

ID=47501110

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12809657.5A Withdrawn EP2791127A1 (fr) 2011-12-13 2012-12-07 Séparation de 5-hydroxyméthylfurfural (hmf) de solutions réactionnelles par distillation à la vapeur d'eau

Country Status (8)

Country Link
EP (1) EP2791127A1 (fr)
JP (1) JP6073362B2 (fr)
KR (1) KR20140101848A (fr)
CN (1) CN103987703B (fr)
BR (1) BR112014013028A2 (fr)
CA (1) CA2856173A1 (fr)
RU (1) RU2014128457A (fr)
WO (1) WO2013087523A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9156802B2 (en) 2011-12-13 2015-10-13 Basf Se Separating off 5-hydroxymethylfurfural (HMF) from reaction solutions by steam distillation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3071599A (en) * 1959-02-25 1963-01-01 Atlas Chem Ind Preparation of hydroxymethyl furfural
US3201331A (en) * 1962-10-17 1965-08-17 Atlas Chem Ind Purification of hydroxymethyl furfural
DE3601281A1 (de) * 1986-01-17 1987-07-23 Sueddeutsche Zucker Ag Verfahren zur herstellung von 5-hydroxymethylfurfural einschliesslich eines kristallinen produktes unter ausschliesslicher verwendung von wasser als loesungsmittel
EP2050742B1 (fr) 2006-03-10 2010-07-07 Furanix Technologies B.V Utilisation d'esters d'acide organique du 5-hydroxyméthylfurfural
EP1834950A1 (fr) 2006-03-10 2007-09-19 Avantium International B.V. Procédé de fabrication d'alkoxyméthylfurfurales et leur utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013087523A1 *

Also Published As

Publication number Publication date
JP2015505848A (ja) 2015-02-26
CN103987703A (zh) 2014-08-13
BR112014013028A2 (pt) 2017-06-13
KR20140101848A (ko) 2014-08-20
CN103987703B (zh) 2016-11-02
WO2013087523A1 (fr) 2013-06-20
CA2856173A1 (fr) 2013-06-20
RU2014128457A (ru) 2016-02-10
JP6073362B2 (ja) 2017-02-01

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