Lignin conversion to fine chemicals

de Albuquerque Fragoso, Danielle Munick (2018) Lignin conversion to fine chemicals. PhD thesis, University of Glasgow.

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The large availability of Kraft lignin as an industrial by-product and its polyaromatic characteristic, is ideal to consider the potential for recycling it into fine chemicals. To depolymerise lignin, solvolysis and hydrogenolysis experiments were performed. This research considered whether the low yields of products (fine chemicals) were related to the low content of β-O-4 bonds or if it was also associated to the dissolution of lignin in the solvent solution employed in the reactions. The type of solvents chosen to check the dissolution effect were those with low cost and were more sustainable than traditional solvents. Water, ethanol, isopropanol (IPA) and acetone were used. The water mixtures were applied in the tests in various proportions (25:75, 50:50, 75:25 solvent/water v:v). Due to their ability to break C-C and C-O bonds in lignin model compounds [1][2], the efficiency of platinum and rhodium in these reactions supported on alumina was also studied. It was found that the non-catalysed (solvolysis) and catalysed reactions showed different selectivities but similar overall yields ~ 10 % wt of monomeric phenols. The difficulty in increasing yields was mainly associated with the highly condensed character of Kraft lignin and re-polymerisation issues.
To achieve an understanding of Kraft lignin depolymerisation, isotopic labelling reactions were completed in the presence of deuterated solvents as well as deuterium gas. This gave information on how Kraft lignin depolymerises, the influence of solvent to products formation and the involvement of hydrogen in the rate determining steps in the reactions. These results have led to an initial mechanistic understanding on how this complex molecule may yield alky-phenolic compounds. It was revealed that the solvent was directly involved in the products’ formation and that they were not generated by simple thermolysis. In addition, the presence of catalysts and hydrogen influenced product formation. The compounds showed different kinetic isotopic values, suggesting that each of these molecules came from individual mechanisms, highlighting the complexity of their formation. This was a relevant study as most of lignin depolymerisation mechanistic insights are based on model compounds and not on lignin itself.
It was of interest to this project to explore not only different catalysts and their relationship to lignin depolymerisation, but also different lignin types. A simple pre-treatment for lignin extraction using sawdust (from oak and birch wood) in a Parr autoclave reactor in the presence of hydrogen, solvent and high temperature was developed. The lignins obtained after the pre-treatment were named parr-lignin and successfully resulted in polyaromatic molecules with less condensed character compared to lignins from Soda or Kraft pulping. Reactions were carried out with these lignins and a sugar-cane lignin.

Different catalytic systems with these lignins were investigated and how depolymerisation was affected by the metal and support used. The catalysts involved in the reactions included platinum, rhodium, nickel and iron. Various supports such as alumina, zirconia and carbon were tested along with the metals described. It was found that the supports were not inert in these experiments presenting catalytic activity. Materials with low surface area (zirconium catalysts) gave a poor performance compared to the others. In addition, nickel, a non-noble metal, showed as good a catalytic effect in the depolymerisation of these lignins as Pt and Rh. The components in the system influenced the reactions to different extents, especially product distribution. The catalysts had different selectivities and the solvents were not only dissolving lignin but also influencing the results.
GPC analysis was performed to give an overview of the condensed level of these lignins and degrees of depolymerisation compared to the original material. GC-MS enabled the identification and quantification of 18 monomeric compounds. The post reaction characterisation of selected alumina catalysts (Pt/Al2O3, Ni/Al2O3 and Al2O3) was performed using XRD, BET, CHN, TPO and Raman Analysis to study the nature of the carbonaceous layer deposited on these materials. The work showed that after reaction the catalysts turned black in colour and the carbon laydown consisted of not only one simple type of carbon, and included graphitic species. The amount of carbon deposited depended on the type of lignin. Oak and birch parr-lignins had the highest and lowest amount of carbon over the catalysts respectively. No obvious trend relating to the type of catalyst, lignin and solvent used to the carbon nature was identified.
This work showed that lignins with less condensed nature were less susceptible to solvolysis and more to hydrogenolysis. For example, sugar-cane lignin gave 3.9% of phenolic compounds in the solvolysis while reaction with Rh/Al2O3 gave 12.9% of products. This indicated that more selective cleavage of bonds were promoted by heterogenous catalysts. The results suggested that some compounds were mainly generated via dealkylation and hydrodeoxygenation, allowing a future possibility to generate target molecules. These results were mainly due to the presence of more labile bonds, vulnerable to hydrogenolysis. Highlighting that prior to depolymerisation, the pre-treatment used to extract lignin must be appropriate to avoid depletion of the alkyl-aryl ether bonds (β-O-4 bonds, especially) relevant for fine chemicals generation.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Additional Information: Supported by: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (scholarship) and financed by CNPq, Ministério da Ciência, Tecnologia, Inovações e Comunicações, Brazil.
Keywords: Lignin, depolymerisation, hydrogenolysis.
Subjects: T Technology > T Technology (General)
T Technology > TP Chemical technology
Colleges/Schools: College of Science and Engineering > School of Chemistry
Supervisor's Name: Jackson, Professor Samuel David
Date of Award: 2018
Depositing User: Miss Danielle Munick de Albuquerque Fragoso
Unique ID: glathesis:2018-30847
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 08 Oct 2018 12:45
Last Modified: 13 Nov 2018 08:00

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