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Refining Lignin for Reliable Chemical Use

This article discusses the need to refine lignin, a by-product of the paper industry, in order to make it a reliable commodity chemical. The authors explore methods to overcome lignin's heterogeneity and achieve consistent chemical properties for various applications.

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Refining Lignin for Reliable Chemical Use

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  1. Our Industry’s Need to Refine Lignin Prior to Use in a Way Similar to Crude C. Cui, R. Sun & D. S. Argyropoulos Departments of Chemistry and Forest Biomaterials North Carolina State University , Raleigh , NC USA Department of Chemistry & Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia. COST Action FP1105 Principles of cell wall assembly – Understanding and Implementation. May 8-9; 2014 Coimbra, Portugal

  2. Our Industry’s Need to Refine Lignin Prior to Use in a Way Similar to Crude Cui, C., Sun, R.,& Argyropoulos, D. S. ; Fractional Precipitation of Softwood Kraft Lignin; Isolation of a Narrow Fractions Common to a Variety of Lignins” ACS Sustainable Chem. Eng., Articles ASAP; Publication Date: January 30, 2014 DOI: 10.1021/sc400545d Argyropoulos, D. S. US Pub. No. : US 2013/0255216A1, Pub Date : Oct.3rd 2013, US Patent Application No,61/601,181, Filed Feb 21 2012.

  3. Kraft Lignin; A Valuable Resource • Kraft lignin is a by-product of the paper industry; • The Kraft process is continuously adjusted/monitored/modified with the aim to produce paper not lignin; • Manufacturing/Seasonal/Geographical & other variations; by definition offer a Heterogeneous/Polydisperse/Irregular & notoriously irreproducible material.

  4. Kraft Lignin; A Valuable Resource • What are key questions/objectives that will significantly (but not incrementally) advance the field? If Kraft lignin is to be used as a valuable chemical resource is it possible to have it Refined & Upgradedto the level of becoming a reliable commodity chemical? Is it possible to arrive at functional kraft lignin polymers/phenolic precursors - of consistent quality & specs on a daily basis ? - of functionality that defines it as a polyol ? - of low Mol. Wt Distribution that defines it as polymeric precursor of defined/controlled reactivity ?

  5. Objectives /Rationale • To develop a technology that allows for some control of the extreme heterogeneity of lignin • To arrive at technical lignins with consistent chemical properties • To tune and control the Functionality of technical lignins Toward Arriving at Fractions of Softwood Kraft Lignin that are Identical in Composition Irrespective of its Manufacturing Details

  6. Selection of Two Different Sources

  7. Kraft Lignin (100 g) 1. Stirred in 1000 mL acetone for 6 h; 2. Filtration. Fractionation Scheme Solid AIKL Supernatant (I) Addition of 250 mL Hexanes Solid ASKL 250mLHex Discarded Supernatant (II) Addition of 750 mL Hexanes Solid ASKL Purified (I) of Uniform Composition Irrespective of its Origin Supernatant (III) • Solvent evaporation; • Re-dissolved in 200 mL of acetone. Acetone solution • Addition of 800 of hexanes; • Filtration ASKL Purified (II)

  8. Superimposed GPC Profiles of Two Softwood Kraft Lignins High H Factor Lignin, 1200-KL Low H Factor Lignin, 600-KL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  9. Superimposed GPC Profiles of the AIKLs of Indulin AT and Domtar Kraft Lignins High H Factor Lignin, 1200-AIKL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  10. Superimposed GPC Profiles of the AIKLs of the two Kraft Lignins High H Factor Lignin, 1200-AIKL Low H Factor Lignin, 600-AIKL The long tailing apparent in AIKL of technical lignins contributes to extreme heterogeneity, increased functionality causing stochastic & irreproducible characteristics

  11. The Case of Kraft Lignin 1 • An Intensively pulped softwood wood aimed at creating Bleachable grade pulp (Very Low Lignin content). • H Factor 1200

  12. Superimposed GPC Profiles of the Whole Kraft Lignin 1 and its Fractions High H Factor Lignin, 1200-KL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  13. Superimposed GPC Profiles of the Whole Kraft Lignin 1 and its Fractions High H Factor Lignin, 1200-KL High H Factor Lignin, 1200-AIKL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  14. Superimposed GPC Profiles of the Whole Kraft Lignin 1 and its Fractions High H Factor Lignin, 1200-KL High H Factor Lignin, 1200-AIKL High H Factor Lignin, 1200-250mLHex Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  15. Superimposed GPC Profiles of the Whole Kraft Lignin 1 and its Fractions High H Factor Lignin, 1200-KL High H Factor Lignin, 1200-AIKL High H Factor Lignin, 1200-250mLHex High H Factor Lignin, 1200-ASKL(I) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  16. Superimposed GPC Profiles of the Whole Kraft Lignin 1 and its Fractions High H Factor Lignin, 1200-KL High H Factor Lignin, 1200-AIKL High H Factor Lignin, 1200-250mLHex High H Factor Lignin, 1200-ASKL(I) High H Factor Lignin, 1200-ASKL(II) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  17. Superimposed GPC Profiles of the Whole Domtar kraft Lignin and its Fractions High H Factor Lignin, 1200-KL High H Factor Lignin, 1200-AIKL High H Factor Lignin, 1200-250mLHex High H Factor Lignin, 1200-ASKL(I) High H Factor Lignin, 1200-ASKL(II) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  18. The Case of Kraft Lignin 2 • An Low Intensity pulped softwood wood aimed at creating Liner board grade pulp, (High Lignin content). • H Factor 600

  19. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  20. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  21. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Low H Factor Lignin, 600-250mLHex Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  22. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Low H Factor Lignin, 600-250mLHex Low H Factor Lignin, 600-ASKL(I) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  23. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Low H Factor Lignin, 600-250mLHex Low H Factor Lignin, 600-ASKL(I) Low H Factor Lignin, 600-ASKL(II) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  24. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Low H Factor Lignin, 600-250mLHex Low H Factor Lignin, 600-ASKL(I) Low H Factor Lignin, 600-ASKL(II) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  25. Superimposed GPC Profiles of the Whole Kraft Lignin 2 and its Fractions Low H Factor Lignin, 600-KL Low H Factor Lignin, 600-AIKL Low H Factor Lignin, 600-250mLHex Low H Factor Lignin, 600-ASKL(I) Low H Factor Lignin, 600-ASKL(II) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  26. Comparison of GPC Profiles of ASKL Purified (I) Emerging form Kraft Lignins 1 & 2 High H Factor Lignin, 1200-KL Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  27. Comparison of GPC Profiles of ASKL Purified (I) Emerging form Kraft Lignins 1 & 2 High H Factor Lignin,1200-ASKL(I) Low H Factor Lignin,600-ASKL(I) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  28. OH Content Comparison for Fraction P(I) from the two Kraft Lignins High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I)

  29. OH Content Comparison for Fraction P(I) from the two Kraft Lignins High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I)

  30. OH Content Comparison for Fraction P(I) from the two Kraft Lignins High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I)

  31. OH Content Comparison for Fraction P(I) from the two Kraft Lignins High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I)

  32. OH Content Comparison for Fraction P(I) from the two Kraft Lignins High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  33. Comparison of Molecular Weight Characteristics High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I)

  34. Comparison of Molecular Weight Characteristics High H Factor Lignin, 1200-ASKL P(I) Low H Factor Lignin, 600-ASKL P(I) Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  35. Fractional Precipitation offers a Continuum of Fractions of Lower Mw & of Progressively Narrow Distribution Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  36. Linear Relations of Vital Functional Groups and Volume Fractions of Hexanes are apparent Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  37. Linear Relations of Vital Functional Groups and Mn are apparent Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  38. By Creating Physical Mixtures of Three Different Softwood Kraft Lignins one is able to Isolate a Common Narrow Fraction Cui, C., Sun, R.,& Argyropoulos, D. S. ; ACS Sustainable Chem. Eng.,  ASAP Publication Date (Web): January 30, 2014 DOI: 10.1021/sc400545d

  39. Outcomes & Opportunities For the first time it is demonstrated that kraft Lignin can be refined. • To distinct, reproducible “cuts” • Such “cuts” are common to various Kraft lignins irrespective of their manufacturing details. • A novel route to lignin upgrading now becomes possible. • A plethora of research opportunities exist in defining the applications for these consistent/reproducible/well defined lignin “cuts”

  40. Strategic Decisions • Treating Lignin with respect will pay off • Focus & capitalize on current limitations • Expand into Hardwood & Biorefinery Lignins • Work with Specific Lignin for specific high value applications • Work with Industry to bring these to further development

  41. Future Context The perusal of Excellent Science is essential to promote the cause of lignin as a valuable chemical resource; The P&P industry needs to adopt an open mind set & work together with the chemical industry; Our responsibility in creating these relations rests in the accountability of our science & the reliability, resilience & economics of our processes.

  42. Acknowledgments • Solvay Specialty Polymers • Domtar Inc. Plymouth NC • King Abdul Aziz University, Centre of Excellence for Advanced Materials Research, Jeddah, Saudi Arabia.

  43. Yields of Fractions

  44. Summative Data on Functional Groups

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