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US 2009/0020112 A1Published application
Method for breaking down cellulose
AssigneeBASF SE
InventorsKlemens Massonne, Giovanni D'Andola, Veit Stegmann, Werner Mormann, Markus Wezstein, Wei Leng, Stephan Freyer
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Abstract
The present invention describes a process for the degradation of cellulose by dissolving the cellulose in an ionic liquid and treating it at elevated temperature, if appropriate in the presence of water.
Claims16
1:
- A process for the degradation of polysaccharides, oligosaccharides or disaccharides or derivatives thereof, wherein the polysaccharide, oligosaccharide or disaccharide or the corresponding derivative is dissolved in at least one ionic liquid and, if appropriate with addition of water, treated at elevated temperature.
2:
- The process according to claim 1, wherein a polysaccharide or a derivative thereof is used as polysaccharide, oligosaccharide or disaccharide or derivative thereof.
3:
- The process according to claim 2, wherein cellulose or a cellulose derivative is used as polysaccharide or derivative thereof.
4:
- The process according to claim 3, wherein cellulose is used as polysaccharide or derivative thereof.
5:
- The process according to claim 1, wherein the ionic liquid or mixture thereof is selected from among the compounds of the formula I,
- [A]+n[Y]n− (I),
- where
- n is 1, 2, 3 or 4;
- [A]+ is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation;
- and
- [Y]n− is a monovalent, divalent, trivalent or tetravalent anion;
- or
- the compounds of the formula II
- [A1]+[A2]+[Y]n− (IIa), where n=2;
- [A1]+[A2]+[A3]+[Y]n− (IIb), where n=3;
- or
- [A1]+[A2]+[A3]+[A4]+[Y]n− (Ic), where n=4, and
- [A1]+, [A2]+, [A3]+ and [A4]+ are selected independently from among the groups specified for [A]+;
- and
- [Y]n− is as defined above.
13 more elements
6:
- The process according to claim 5, wherein [A]+ is a cation selected from among the compounds of the formulae (IIIa) to (IIIy)
- and oligomers comprising these structures, where
- the radical R is hydrogen or a carbon-comprising organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical which has from 1 to 20 carbon atoms and may be unsubstituted or be interrupted or substituted by from 1 to 5 heteroatoms or functional groups;
- and
- the radicals R1 to R9 are each, independently of one another, hydrogen, a sulfo group or a carbon-comprising organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical which has from 1 to 20 carbon atoms and may be unsubstituted or be interrupted or substituted by from 1 to 5 heteroatoms or functional groups, where the radicals R1 to R9 which are bound to a carbon atom (and not to a heteroatom) in the abovementioned formulae (III) can additionally be halogen or a functional group;
- or two adjacent radicals from the group consisting of R1 to R9 may together also form a divalent, carbon-comprising organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical which has from 1 to 30 carbon atoms and may be unsubstituted or be interrupted or substituted by from 1 to 5 heteroatoms or functional groups.
3 more elements
7:
- The process according to claim 5, wherein [Y]n− is an anion selected from among
- the group of halides and halogen-comprising compounds of the formulae:
- F—, Cl—, Br—, I—, BF4—, PF6—, CF3SO3—, (CF3SO3)2N—, CF3CO2—, CCl3CO2—, CN—, SCN—, OCN—
- the group of sulfates, sulfites and sulfonates of the general formulae:
- SO42—, HSO4—, SO32—, HSO3—, RaOSO3—, RaSO3—
- the group of phosphates of the general formulae PO43—, HPO2—, H2PO4—, RaPO42—, HRaPO4—, RaRbPO4—
- the group of phosphonates and phosphinates of the general formulae:
- RaHPO3—,RaRbPO2—, RaRbPO3—
- the group of phosphites of the general formulae:
- PO33—, HPO32—, H2PO3—, RaPO32—, RaHPO3—, RaRbPO3—
- the group of phosphonites and phosphinites of the general formulae:
- RaRbPO2—, RaHPO2—, RaRbPO—, RaHPO—
- the group of carboxylic acids of the general formula:
- RaCOO—
- the group of borates of the general formulae:
- BO33—, HBO32—, H2BO3—, RaRbBO3—, RaHBO3—, RaBO32—, B(ORa)(ORb)(ORc)(ORd)—, B(HSO4)—, B(RaSO4)—
- the group of boronates of the general formulae:
- RaBO22—, RaRbBO—
- the group of silicates and silicic esters of the general formulae:
- SiO44—, HSiO43—, H2SiO42—, H3SiO4—, RaSiO43—, RaRbSiO42—, RaRbRcSiO4—, HRaSiO42—, H2RaSiO4—, HRaRbSiO4—
- the group of alkylsilane and arylsilane salts of the general formulae:
- RaSiO33—, RaRbSiO22—, RaRbRcSiO—, RaRbRcSiO3—, RaRbRcSiO2—, RaRbSiO32—
- the group of carboximides, bis(sulfonyl)imides and sulfonylimides of the general formulae:
- the group of methides of the general formula:
- where the radicals Ra, Rb, Rc and Rd are each, independently of one another, hydrogen, C1-C30-alkyl, C2-C18-alkyl which may optionally be interrupted by one or more nonadjacent oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, C6-C14-aryl, C5-C12-cycloalkyl or a five- or six-membered, oxygen-, nitrogen- and/or sulfur-comprising heterocycle, where two of them may together form an unsaturated, saturated or aromatic ring which may optionally be interrupted by one or more oxygen and/or sulfur atoms and/or one or more unsubstituted or substituted imino groups, where the radicals mentioned may each be additionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles.
22 more elements
8:
- The process according to any claim 6, wherein [A]+ is a cation selected from the group consisting of the compounds IIIa, IIIe, IIIf;
- IIIg, IIIg′, IIIh, IIIi, IIIj, IIIj′, IIIk, IIIk′, IIIl, IIIm, IIIm′, IIIn and IIIn′.
9:
- The process according to claim 6, wherein [A]+ is a cation selected from the group consisting of the compounds IIIa, IIIe and IIIf.
10:
- The process according to claim 7, wherein [Y]n− is an anion selected from the group consisting of halides and halogen-comprising compounds, the group consisting of carboxylic acids, the group consisting of SO42—, SO32—, RaOSO3— and RaSO3— and the group consisting of PO43— and RaRbPO4—.
11:
- The process according to claim 9, wherein [Y]n− is an anion selected from the group consisting of HSO4—, HPO42—, H2PO4— and HRaPO4—.
12:
- The process according to any claim 1, wherein the concentration of polysaccharide, oligosaccharide or disaccharide or derivative thereof in the ionic liquid is in the range from 0.1 to 50% by weight, based on the total weight of the solution.
13:
- The process according to claim 12, wherein water is added.
14:
- The process according to claim 1, wherein the treatment is carried out without addition of water.
15:
- The process according to claim 1 wherein the hydrolysis is carried out at a temperature in the range from 0 to 200° C.
16:
- The process according to claim 1, wherein the degradation is quenched by addition of a solvent in which the degradation products of the polysaccharide are not soluble.