METHOD FOR PRODUCING GLUCOSE BY ENZYMATIC HYDROLYSIS OF CELLULOSE THAT IS OBTAINED FROM MATERIAL CONTAINING LIGNO-CELLULOSE USING AN IONIC LIQUID THAT COMPRISES A POLYATOMIC ANION

• US 20100081798A1
• Filed: 01/22/2008
• Published: 04/01/2010
• Est. Priority Date: 01/23/2007
• Status: Abandoned Application

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Schroeder, Hartwig, Massonne, Klemens, Freyer, Stephan, D'Andola, Giovanni, Balensiefer, Tim
• Application Number:
  US12/523,740
• Publication Number:
  US 20100081798A1
• Time in Patent Office: Days
• US Class Current: 530/500
• CPC Class Codes: C12P 19/02 Monosaccharides 2-ketogulonic acid C12P7/60
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

The present invention relates to a process for preparing glucose from a lignocellulose-comprising starting material, in which this is firstly treated with an ionic liquid and subsequently subjected to an enzymatic hydrolysis. The invention further relates to a process for preparing microbial metabolites, especially ethanol, in which the glucose obtained is additionally subjected to a fermentation.

Claims

1. A process for preparing a glucose product from a lignocellulose material, in which

a lignocellulose-comprising starting material is provided and treated with a liquid treatment medium which comprises an ionic liquid whose anions are selected from among polyatomic anions,

a cellulose-enriched material is isolated from the treated material and

the cellulose-enriched material is subjected to an enzymatic hydrolysis.

2. The process according to claim 1, wherein at least one ionic liquid selected from among

(A) salts of the general 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 multiatomic, monovalent, divalent, trivalent or tetravalent anion or a mixture of these anions;

(B) mixed salts of the general formulae (II.a), (II.b) and (II.c)

[A¹]⁺[A²]⁺[Y]ⁿ⁻

 

 

(II.a), where n=2,

[A¹]⁺[A²]⁺[A³]⁺[Y]ⁿ⁻

 

 

(II.b), where n=3,

[A¹]⁺[A²]⁺[A³]⁺[A⁴]⁺[Y]ⁿ⁻

 

 

(II.c), where n=4,

where [A¹]⁺, [A²]⁺, [A³]⁺ and [A⁴]⁺ are selected independently from among the groups mentioned for [A]⁺ and [Y]ⁿ⁻

is as defined under (A);

or

(C) mixed salts of the general formulae (III.a) to (III.j)

[A¹]⁺[A²]⁺[A³]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(III.a), where n=4,

[A¹]⁺[A²]⁺[M¹]⁺[M²]⁺[Y]ⁿ⁻

 

 

(III.b), where n=4,

[A¹]⁺[M¹]⁺[M²]⁺[M³]⁺[Y]ⁿ⁻

 

 

(III.c), where n=4,

[A¹]⁺[A²]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(III.d), where n=3,

[A¹]⁺[M¹]⁺[M²]⁺[Y]ⁿ⁻

 

 

(III.e), where n=3,

[A¹]⁺[M¹]⁺[Y]ⁿ⁻

 

 

(III.f), where n=2,

[A¹]⁺[A²]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(III.g), where n=4,

[A¹]⁺[M¹]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(III.h), where n=4,

[A¹]⁺[M⁵]³⁺[Y]ⁿ⁻

 

 

(III.i), where n=4,

[A¹]⁺[M⁴]²⁺[Y]ⁿ⁻

 

 

(III.j), where n=3,

where [A¹]⁺, [A²]⁺ and [A³]⁺ are selected independently from among the groups mentioned for [A]⁺, [Y]ⁿ⁻

is as defined under (A) and [M¹]⁺, [M²]⁺, [M³]⁺ are monovalent metal cations, [M⁴]²⁺ is a divalent metal cation and [M⁵]³⁺ is a trivalent metal cation,

is used.

3. The process according to either claim 1 or 2, wherein at least one ionic liquid having at least one cation selected from among compounds of the formulae (IV.a) to (IV.z),

4. The process according to claim 3, wherein at least one ionic liquid having at least one cation selected from among imidazolium ions of the formula (IV.e) is used.

5. The process according to any of the preceding claims, wherein at least one ionic liquid having at least one anion selected from:

the group of pseudohalides and halogen-comprising compounds of the formulae;

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⁻

, R^cOSO₃⁻

, R^cSO₃⁻

;

the group of phosphates of the general formulae;

PO₄³⁻

, HPO₄²⁻

, H₂PO₄⁻

, R^cPO₄²⁻

, HR^cPO₄⁻

, R^cR^dPO₄⁻

;

the group of phosphonates and phosphinates of the general formulae;

R^cHPO₃⁻

,R^cR^dPO₂⁻

, R^cR^dPO₃⁻

;

the group of phosphites of the general formulae;

PO₃³⁻

, HPO₃²⁻

, H₂PO₃⁻

, R^cPO₃²⁻

, R^cHPO₃⁻

, R^cR^dPO₃⁻

;

the group of phosphonites and phosphinites of the general formulae;

R^cR^dPO₂⁻

, R^cHPO₂⁻

, R^cR^dPO⁻

, R^cHPO⁻

;

the group of carboxylic acids of the general formula;

R^cCOO⁻

;

anions of hydroxycarboxylic acids and sugar acids;

saccharinates (salts of o-benzoic sulfimide);

the group of borates of the general formulae;

BO₃³⁻

, HBO₃²⁻

, H₂BO₃⁻

, R^cR^dBO₃⁻

, R^cHBO₃⁻

, R^cBO₃²⁻

,

B(OR^c)(OR^d)(OR^e)(OR^f)⁻

, B(HSO₄)₄⁻

, B(R^cSO₄)₄⁻

;

the group of boronates of the general formulae;

R^cBO₂²⁻

, R^cR^dBO⁻

;

the group of carbonates and carbonic esters of the general formulae;

HCO₃⁻

, CO₃²⁻

, R^cCO₃⁻

;

the group of silicates and salicic esters of the general formulae;

SiO₄⁴⁻

, HSiO₄³⁻

, H₂SiO₄²⁻

, H₃SiO₄⁻

, R^cSiO₄³⁻

, R^cR^dSiO₄²⁻

, R^cR^dR^eSiO₄⁻

, HR^cSiO₄²⁻

, H₂R^cSiO₄⁻

, HR^cR^dSiO₄⁻

;

the group of alkylsilanolates and arylsilanolates of the general formulae;

R^cSiO₃³⁻

, R^cR^dSiO₂²⁻

, R^cR^dR^eSiO⁻

, R^cR^dR^eSiO₃⁻

, R^cR^dR^eSiO₂⁻

, R^cR^dSiO₃²⁻

;

the group of carboxylmides, bis(sulfonyl)imides and sulfonylimides of the general formulae;

6. The process according to any of the preceding claims, wherein at least one ionic liquid having at least one anion selected from the group of pseudohalides and halogen-comprising compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates or the group of phosphates is used.

7. The process according to any of the preceding claims, wherein the lignocellulose-comprising starting material is subjected to mechanical comminution before or during the treatment with the ionic liquid.

8. The process according to any of the preceding claims, wherein the lignocellulose-comprising starting material is solubilized in the treatment medium comprising the ionic liquid.

9. The process according to any of the preceding claims, wherein the cellulose-enriched material is isolated from the treated material by addition of a precipitant (P1) and subsequent separation into a cellulose-enriched fraction and a cellulose-depleted fraction.

10. The process according to claim 9, wherein a solvent or solvent mixture which in combination with the ionic liquid is capable of dissolving lignin is used as precipitant (P1).

11. The process according to either claim 9 or 10, wherein the precipitant (P1) is selected from among organic solvents or solvent mixtures which are at least partially, preferably completely, miscible with the ionic liquid used for the treatment of the lignocellulose material.

12. The process according to any of claims 9 to 11, wherein the mixture obtained in the precipitation is fractionated to give a cellulose-enriched fraction and a liquid output (O1) which is enriched in lignin.

13. The process according to claim 12, wherein the liquid output (O1) is subjected to a separation into a fraction (IL1) comprising essentially the ionic liquid, a fraction (Lig1) comprising essentially the lignin and a fraction (P1) comprising essentially the precipitant.

14. The process according to claim 13, wherein at least part of the precipitant (P1) is firstly separated off by evaporation, a precipitant (P2) is added to the composition remaining after (P1) has been separated off, resulting in the lignin being at least partly precipitated, and a separation into a fraction (Lig1) comprising essentially the lignin and a fraction (IL1) comprising essentially the ionic liquid is subsequently carried out.

15. The process according to claim 13, wherein the fraction (IL1) comprising essentially the ionic liquid is reused for the treatment of the lignocellulose-comprising starting material.

16. The process according to any of the preceding claims, wherein the cellulose-enriched material is subjected to a treatment to remove ionic liquid still comprised.

17. The process according to claim 16, wherein the cellulose-enriched material is subjected to washing with a liquid washing medium.

18. The process according to claim 17, wherein the treatment of the cellulose-enriched material with a washing medium is carried out at a temperature of at least 40°

C., preferably at least 60°

C., in particular at least 80°

C.

19. The process according to either claim 17 or 18, wherein the washing medium comprises water or consists of water.

20. A process for producing a microbial metabolite having at least two carbon atoms, which comprises fermentation of glucose obtained by a process according to any of claims 1 to 19.

21. The process according to claim 20, wherein the metabolite comprises ethanol.

22. The process according to any of claims 1 to 21 comprising the following steps:

a) treatment of the lignocellulose-comprising starting material with a liquid treatment medium comprising an ionic liquid, the starting material being solubilized in the treatment medium,

b) precipitation of the cellulose from the solubilizate obtained in step a) by addition of a first precipitant (P1) which in combination with the ionic liquid is capable of dissolving lignin,

c) separation into a cellulose-enriched fraction and a first liquid output (O1) which is enriched in lignin,

d) separation of the output (O1) into a fraction (IL1) comprising essentially the ionic liquid, a fraction (Lig1) comprising essentially the lignin and a fraction comprising essentially the precipitant (P1), with (IL1) being recirculated at least partly to step a) and (F1) being recirculated at least partly to step b),

e) treatment of the cellulose-enriched fraction to remove ionic liquid still comprised and precipitant (P1) possibly still comprised with an aqueous washing medium,

f) separation into a purified cellulose-enriched fraction and a second liquid output (O2),

g) separation of the output (O2) into

a fraction (IL2) which comprises essentially the removed ionic liquid and is at least partly recirculated to step a),

a fraction which comprises essentially the precipitant (P1) and is at least partly recirculated to step b),

a water-comprising fraction which is at least partly recirculated to step e),

h) use of the cellulose-enriched fraction obtained in step f) in the enzymatic hydrolysis.

23. The process according to claim 22, wherein, in step d), at least part of the precipitant (P1) is firstly separated off by evaporation, a second precipitant (P2) is added to the composition remaining after (P1) has been separated off, the lignin being at least partly precipitated, and a separation into a fraction (Lig1) comprising essentially the lignin and a fraction (IL1) comprising essentially the ionic liquid is subsequently carried out.

24. The process according to any of the preceding claims, wherein enzymes which are capable of degrading hemicellulose to sugars, especially xylose, are additionally used for the enzymatic hydrolysis.

25. The process according to any of claims 22 to 24, wherein the glucose product obtained in step h) is subjected to a separation into a fraction comprising essentially the glucose and a fraction comprising hemicellulose and/or lignin (=step i).

26. The process according to any of claims 22 to 25 for producing a microbial metabolite having at least two carbon atoms, which additionally comprises

k) fermentation of the glucose product obtained in step h) or step i).

27. The process according to claim 26, wherein ethanol is obtained as microbial metabolite.

28. A glucose product which can be obtained by a process as defined in any of claims 1 to 25.

29. A lignin product which can be obtained by a process as defined in any of claims 1 to 25.