Methods for preparing thermally stable lignin fractions

• US 9,683,005 B2
• Filed: 05/02/2014
• Issued: 06/20/2017
• Est. Priority Date: 05/03/2013
• Status: Active Grant

• Current Assignee: Virdia Ltd
• Original Assignee: Virdia, Inc. (Stora Enso Oyj)
• Inventors: Hallac, Bassem, Rotem, Perry, Jansen, Robert, Lawson, James Alan, Lapidot, Noa
• Primary Examiner(s): McAvoy, Ellen
• Assistant Examiner(s): GRAHAM, CHANTEL LORAN
• Application Number:
  US14/787,756
• Publication Number:
  US 20160102113A1
• Time in Patent Office: 1,145 Days
• Field of Search: 1062731, 423445 R, 4234471, 44436, 507106, 521155, 523456, 530500, 530507, 554 1, 554213, 560 1, 562400, 568303, 568426, 568449, 568700, 568799, 585469, 585639, 585733
• CPC Class Codes: C07G 1/00 Lignin; Lignin derivatives
• CPC Class Codes: D21C 11/0007 Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for volatile compounds obtained by decomposition of spent liquors in order to regenerate them D21C11/125; compounds obtained by fractionating the liquors in order to regenerate them D21C11/0042
• CPC Class Codes: D21C 3/20 with organic solvents or in solvent environment

Abstract

The present invention relates to fractions of high purity lignin which are thermally stable, and to methods of producing said fractions from lignocellulosic material.

Claims

1. A lignin composition comprising lignin, wherein the composition is characterized by a consistent glass transition temperature (Tg) as determined by two consecutive differential scanning calorimetry (DSC) runs of the same lignin portion according to DIN 53765-1994, wherein a first Tg is measured during a first DSC run, a second Tg is measured during a second DSC run, and the difference between the first Tg and the second Tg is less than 10°

C.

2. The composition of claim 1, wherein the difference between the first Tg and the second Tg is less than 5°

C.

3. The composition of claim 1, wherein the second glass transition temperature is above 160°

C.

4. The composition of claim 1, wherein the second glass transition temperature is below 100°

C.

5. The composition of claim 1, further comprising a marker molecule at a concentration of at least 100 ppb.

6. The composition of claim 5, wherein the marker molecule is selected from the group consisting of isopropanol, ethyl acetate, ethyl formate, dichloromethane, hexanol, furfural, hydroxy-methyl furfural, 2,3,5 trimethyl furan, p-hydroxyphenoxyacetic acid, 4-hydroxy-3,5-dimethoxyphenyl acetic acid, methylethyl ketone, methylpropenyl ketone, 3-(2-furyl)-3-penten-2-one, 3-methyl-2-penten-4-one, 3,4-dimethyl-4-hexene-one, 5-ethyl-5-hexene-3-one, 5-methyl-4-heptene-3-one, o-hydroxyanisole, 3-ethyl-4-methyl-3-penten-2-one, 3,4,4-trimethyl-2-cyclohexene-1-one, 2′

-hydroxy-4′

,5′

-dimethylacetophenone, 1-(4-hydroxy-3-methoxyphenyl)propane, methanol, galacturonic acid, dehydroabietic acid, glycerol, fatty acids and resin acids.

7. The composition of claim 1, further comprising volatile sulfur compounds in an amount less than 0.1 times an amount found in Kraft lignin.

8. The composition of claim 1, further comprising ash in an amount less than 0.5%.

9. The composition of claim 1, further comprising sulfur in an amount less than 700 ppm.

10. The composition of claim 1, further comprising soluble carbohydrates in an amount less than 0.5%.

11. A method for fractionating lignin, the method comprising:

(i) contacting a sample comprising solid lignin and less than 1% weight/weight carbohydrates with an organic solvent to form a biphasic mixture, wherein the mixture comprises;

(a) a remainder solid comprising a first fraction of the lignin, wherein the first fraction is designated as a solvent-insoluble lignin fraction; and

(b) a liquid solution comprising the solvent and a second fraction of the lignin, wherein the second fraction is designated as a solvent-soluble lignin fraction; and

(ii) spatially separating the solvent-insoluble lignin fraction from the solvent-soluble lignin fraction;

wherein the solvent-insoluble lignin fraction and the solvent-soluble lignin fraction have different glass transition temperatures.

12. The method of claim 11, wherein the solvent comprises at least one organic molecule having up to 5 carbon atoms and at least one heteroatom.

13. The method of claim 11, wherein the contacting occurs at 20 to 50°

C.

14. The method of claim 11, wherein the contacting occurs for 1 to 10 hours.

15. The method of claim 11, wherein the spatial separating comprises filtration or decantation of the solvent from the solvent-insoluble lignin fraction.

16. The method of claim 11, further comprising evaporating the solvent from the solvent-soluble lignin fraction and drying each fraction to obtain a dry solid solvent-soluble lignin fraction and a dry solid solvent-insoluble lignin fraction;

wherein the two dry solid lignin fractions have different molecular weights as determined by gel permeation chromatography and different glass transition temperatures.

17. The method of claim 11, wherein at least one of the lignin fractions has a consistent glass transition temperature (Tg) as determined by two consecutive differential scanning calorimetry (DSC) runs of the same lignin portion according to DIN 53765-1994, wherein a first Tg is measured during a first DSC run, a second Tg is measured during a second DSC run, and the difference between the first Tg and the second Tg is less than 10°

C.

18. The method of claim 11, wherein the solvent-soluble lignin fraction has a different glass transition temperature than the solvent-insoluble lignin fraction.

19. The method of claim 11, wherein the solvent is selected from a group consisting of methanol, ethanol, isopropanol, ethyl acetate, ethyl formate, dichloromethane, and any mixture thereof.

20. A method for producing high purity lignin from a biomass, comprising:

(i) removing hemicellulose sugars from the biomass, thereby obtaining a lignin-containing remainder;

wherein the lignin-containing remainder comprises lignin and cellulose;

(ii) contacting the lignin-containing remainder with a lignin extraction solution to produce a lignin extract and a cellulosic remainder;

wherein the lignin extraction solution comprises a limited-solubility solvent, an organic acid, and water, wherein the limited-solubility solvent and the water form an organic phase and an aqueous phase; and

(iii) separating the lignin extract from the cellulosic remainder;

wherein the lignin extract comprises lignin dissolved in the limited-solubility solvent;

and further comprising one, two, three or four additional step(s) selected from;

(iv) distilling or flash evaporating the lignin extract, thereby removing the bulk of the limited-solubility solvent from the lignin extract to obtain a solid lignin;

(v) heating the solid lignin, thereby removing trace limited-solubility solvent or water from the solid lignin;

(vi) applying a vacuum to the solid lignin, thereby removing trace limited-solubility solvent or water from the solid lignin; and

(vii) contacting the solid lignin with an organic solvent to form a biphasic mixture, wherein the mixture comprises;

(a) a remainder solid comprising a first fraction of the lignin, wherein the first fraction is designated as a solvent-insoluble lignin fraction; and

(b) a liquid solution comprising the solvent and a second fraction of the lignin, wherein the second fraction is designated as a solvent-soluble lignin fraction.