Lignin fractionation and fabrication for quality carbon fiber

Patent metadata

Field	Value
Publication number	US-11840776-B2
Application number	US-201916975667-A
Country	US
Kind code	B2
Filing date	Feb 26, 2019
Priority date	Feb 26, 2018
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

A method of producing carbon fibers includes (a) treating lignin to produce a precursor lignin having an increased uniformity. The increased uniformity is defined by (i) an increased linear structure as evidenced by an increased percentage of linkages selected from uncondensed β-O-4′ interunitery linkages or condensed β-5′ linkages, (ii) a reduced polydispersity index (PDI), or (iii) an increased amount of multiple intermolecular hydrogen bonding relative to the lignin prior to treating. In addition, the method includes (b) forming precursor fibers from the precursor lignin. Further, the method includes (c) subjecting the precursor fibers to thermostabilization or carbonization to produce the carbon fibers.

First claim

What is claimed is:

1. A method of producing carbon fibers, the method comprising:
(a) treating lignin to produce a precursor lignin having an increased uniformity defined by (i) an increased linear structure as evidenced by an increased percentage of linkages selected from uncondensed β-O-4′ interunitary linkages, condensed β-5′ linkages, or a combination thereof, and (ii) a reduced polydispersity index (PDI), wherein the PDI is defined as the weight average molecular weight divided by the number average molecular weight;
(b) forming precursor fibers from the precursor lignin; and
(c) subjecting the precursor fibers to thermostabilization, carbonization, or both to produce the carbon fibers,
wherein (a) comprises:
fractioning the lignin to provide a water soluble fraction and a water insoluble fraction, wherein fractionating the lignin to provide the water soluble fraction and the water insoluble fraction comprises:
subjecting the lignin to an enzyme-mediator system, wherein the enzyme-mediator system comprises the enzyme laccase, and a mediator selected from the group consisting of 1-hydroxy benzotriazolehydrate (HBT), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS), acetosyringone, phenol, and combinations thereof; and
reducing the polydispersity of the water insoluble fraction by utilizing dialysis to produce, from the water insoluble fraction, a higher molecular weight portion and a lower molecular weight portion, wherein the higher molecular weight portion has a higher average molecular weight than the lower molecular weight portion, and wherein the polydisperisty of the higher molecular weight portion is less than that of the water insoluble fraction, wherein the precursor lignin comprises at lest a portion of the higher molecular weight portion,

wherein reducing the polydispersity of the water insoluble fraction comprising producing the higher molecular weight fraction having a polydispersity of from about 2-3.

2. The method of claim 1 , wherein the enzyme-mediator system comprises the enzyme laccase, and the mediator comprises 1-hydroxy benzotriazolehydrate (HBT).

3. The method of claim 1 , wherein subjecting the lignin to the enzyme-mediator system further comprises producing a buffered solution of the lignin, adding the enzyme and the mediator to the buffered solution of the lignin, stirring for a time period, and separating the water insoluble fraction from the stirred solution.

4. The method of claim 1 , wherein the precursor lignin has:
a weight average molecular weight in a range of from about 1 to about 20, from about 3 to about 20, from about 1 to about 10, or greater than, less than, or equal to about 20, 10, or 1 K g/mol;
a polydispersity index (PDI), defined as the weight average molecular weight divided by the number average molecular weight, of less than or equal to 5, 4, 3, 2, or 1;
a percentage of interunitary linkages selected from uncondensed β-O-4′ interunitary linkages and condensed β-5′ interunitary linkages that is greater than or equal to about 10%;
an amount of multiple intermolecular hydrogen bonding that is increased relative to the lignin prior to treating at (a);
or a combination thereof.

5. The method of claim 1 , wherein the precursor fibers at (b) have improved spinnability relative to precursor fibers formed in the same manner but without treating the lignin at (a) or absent the lignin, the improved spinnability evidenced by a narrower diameter distribution of the carbon fibers obtained at (c).

6. The method of claim 1 , wherein forming precursor fibers from the precursor lignin comprises:
combining the precursor lignin with a guest polymer and optionally single walled carbon nanotubes (SWCNT); and
electrospinning to produce the precursor fibers.

7. The method of claim 6 , wherein the guest polymer comprises polyacrylonitrile (PAN).

8. The method of claim 7 , wherein the carbon fibers have: a reduced elastic modulus, as measured by nanoindentation, that is greater than or about equal to same carbon fibers produced with pure PAN.

9. The method of claim 1 , wherein the carbon fibers have:
an average diameter of less than or equal to about 1300 nm;
an increased content of pre-graphitic turbostratic structure relative to carbon fibers made in the same manner but without treating the lignin or absent the lignin, as evidenced by a distance between interfacial crystallite layers, as measured by d hkl determined by X-ray diffraction (XRD), that is less than or equal to about 0.390 nm;
a crystallite size, UK as measured by XRD, that is at least 20% greater than a crystallite size of carbon fibers made in the same manner but without treating the lignin or absent the lignin;
an increased crystallite content, as evidenced by an integration ratio of G and D bands (G/D ratio), as measured by Raman spectroscopy, that is at least 20% greater than a G/D ratio of carbon fibers made in the same manner but without treating the lignin or absent the lignin;
a reduced elastic modulus, as measured by nanoindentation, that is at least 30% greater than a reduced elastic modulus of carbon fibers made in the same manner but without treating the lignin or absent the lignin; or
a combination thereof.

10. The method of claim 1 , wherein (c) comprises subjecting the precursor fibers to thermostabilization to produced thermostabilized precursor fibers, wherein the thermostabilized precursor fibers have a glass transition temperature, T g , that is lower than a glass transition temperature of thermostabilized fibers made in the same manner, but without treating the lignin.

11. The method of claim 1 , wherein the higher molecular weight portion has an average molecular weight (M n ) of greater than or equal to about 20,000 g/mol.

12. The method of claim 1 , wherein utilizing dialysis comprises dialyzing a solution of the lignin comprising the water insoluble fraction with dialysis apparatus having a molecular weight cutoff of greater than or equal to about 6-8 K g/mol.

13. The method of claim 1 , wherein (b) forming the precursor fibers from the precursor lignin further comprises lyophilizing the precursor lignin and/or grinding the precursor lignin prior to combining the precursor lignin with a guest polymer.

14. The method of claim 1 , wherein the carbon fibers have an average diameter of less than or equal to about 350 nm.

15. A method of producing carbon fibers, the method comprising:
(a) treating lignin to produce a precursor lignin having an increased uniformity defined by (i) an increased linear structure as evidenced by an increased percentage of linkages selected from uncondensed β-O-4′ interunitary linkages, condensed β-5′ linkages, or a combination thereof, and (ii) a reduced polydispersity index (PDI), wherein the PDI is defined as the weight average molecular weight divided by the number average molecular weight;
(b) forming precursor fibers from the precursor lignin; and
(c) subjecting the precursor fibers to thermostabilization, carbonization, or both to produce the carbon fibers,
wherein (a) comprises:
fractioning the lignin to provide a water soluble fraction and a water insoluble fraction, wherein fractionating the lignin to provide the water soluble fraction and the water insoluble fraction comprises:
subjecting the lignin to an enzyme-mediator system, wherein the enzyme-mediator system comprises the enzyme laccase, and a mediator selected from the group consisting of 1-hydroxy benzotriazolehydrate (HBT), 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), acetosyringone, phenol, and combinations thereof; and
reducing the polydispersit

Assignees

• Texas A & M Univ Sys

Inventors

• Yuan Joshua Shuhua
• Li Qiang

Classifications

• D01F9/17 Primary

  from lignin · CPC title

• C07G1/00

  Low-molecular-weight derivatives of lignin (high-molecular-weight derivatives of lignin {C08H6/00}) · CPC title

• D01D5/003

  the material being a polymer solution or dispersion (D01D5/0053 takes precedence) · CPC title

• C08H6/00

  Macromolecular compounds derived from lignin, e.g. tannins, humic acids · CPC title

• D01F1/10

  Other agents for modifying properties · CPC title