| 1. |
|
|
| 2. |
|
|
| 3. |
|
|
| 4. |
- Ahlbom, Anders, 1993
(författare)
-
Hydrothermal Liquefaction of Kraft Lignin - The influence of capping agents and residence time
- 2021
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the context of exploring alternatives to replace fossil resources, lignin has been acknowledged as a renewable source of various aromatic compounds that have the potential of being precursors to chemicals as well as fuel additives. Originating from lignocellulosic biomass such as wood, lignin is an amorphous polymer with a high content of aromatic units and, in order to harness these units, it must be depolymerised. A major problem with current depolymerisation techniques, however, is that lignin repolymerises after being depolymerised, and forms an undesirable char fraction. The addition of capping agents and fine-tuning the reaction conditions can be used to mitigate such formation of char. This work has investigated the depolymerisation of kraft lignin in hydrothermal conditions under varying temperatures (290-335 °C), residence times (1-12 min) and charges of isopropanol (IPA/dry lignin, 0-4.9) which, aside from being a co-solvent, was hypothesised as acting as a capping agent. The influence of these reaction parameters on the molecular weights, yields and elemental compositions of the products was studied, along with changes in the molecular structure compared to the starting lignin. The product is a suspension of solid material, i.e. char, in an aqueous phase and thus any desired organic liquid phase requires extraction from the aqueous product. While the yield of char increased with temperature and residence time, it decreased with increasing isopropanol loading, suggesting that the isopropanol does in fact act as a capping agent. Most of the lignin forms a water-soluble fraction that precipitates when the aqueous product phase is acidified, thereby forming the precipitated solids fraction (PS). The components remaining dissolved after acidification of the product phase are known as acid soluble organics (ASO). A portion of the ASO fraction was aromatic monomers, with guaiacol dominating: this result was expected since the lignin was sourced from softwood. The amount of such monomers increased with residence time in the reactor. Molecular weight analyses showed a rapid depolymerisation of the lignin within 1 min of hydrothermal liquefaction (HTL) treatment via a significant decrease in the molecular weight of all product fractions: char, PS and ASO. Moreover, the carbon-oxygen inter-unit linkages were found to break in this timeframe as well. The repolymerisation reactions started to exceed depolymerisation between residence times of 4 and 12 min, causing the weight average molecular weight (Mw) to increase again. Although minimising the residence time allows the char yield and Mw to be kept low, more monomers were formed at longer residence times. This calls for careful tuning of the residence time in the HTL of kraft lignin.
|
|
| 5. |
- Ahlbom, Anders, 1993, et al.
(författare)
-
On the hydrothermal depolymerisation of kraft lignin using glycerol as a capping agent
- 2023
-
Ingår i: Holzforschung. - : Walter de Gruyter GmbH. - 1437-434X .- 0018-3830. ; 77:3, s. 159-169
-
Tidskriftsartikel (refereegranskat)abstract
- Depolymerisation of kraft lignin under hydrothermal conditions was investigated at short residence times (1–12 min) with glycerol being used as a capping agent. The weight average molecular weight (M w) of the products decreased within the first minute of residence time, with the inter-unit ether linkages breaking accordingly. Furthermore, the M w of the product fractions decreased at increasing residence times, while the char yield increased. Short residence times thus appear to be beneficial for mitigating the formation of char. Also, addition of NaOH reduced the yield of char. Although the addition of glycerol caused a decrease in the M w of the products, it seemed to increase the yield of char and therefore might not be a suitable capping agent for kraft lignin depolymerisation.
|
|
| 6. |
- Ahlbom, Anders, 1993, et al.
(författare)
-
Towards understanding kraft lignin depolymerisation under hydrothermal conditions
- 2021
-
Ingår i: Holzforschung. - : Walter de Gruyter GmbH. - 1437-434X .- 0018-3830. ; 76:1, s. 37-48
-
Tidskriftsartikel (refereegranskat)abstract
- Kraft lignin depolymerisation using hydrothermal liquefaction suffers from the formation of char, resulting in a decreased product yield as well as causing operational problems. While this may be mitigated by the addition of capping agents such as phenol and isopropanol, other reaction parameters, for example reaction time and temperature, are also important for the product yields. In this work, the effect of short reaction times on the hydrothermal liquefaction of kraft lignin in an alkaline water and isopropanol mixture was investigated at 1-12 min and 290 °C. The results show that there were swift initial reactions: the major ether bonds in the lignin were broken within the first minute of reaction, and the molecular weight of all product fractions was halved at the very least. Longer reaction times, however, do not cause as pronounced structural changes as the initial reaction, indicating that a recalcitrant carbon-carbon skeleton remained in the products. Nevertheless, the yields of both char and monomers increased slowly with increasing reaction time. The swift initial depolymerising reactions were therefore followed by slower repolymerisation as well as a slow formation of monomers and dimers, which calls for careful tuning of the reaction time.
|
|
| 7. |
- Ahlbom, Anders, 1993, et al.
(författare)
-
Using guaiacol as a capping agent in the hydrothermal depolymerisation of kraft lignin
- 2023
-
Ingår i: Nordic Pulp and Paper Research Journal. - 2000-0669 .- 0283-2631. ; 38:4, s. 619-631
-
Tidskriftsartikel (refereegranskat)abstract
- The depolymerisation of softwood kraft lignin was investigated, under hydrothermal conditions at 290 °C and 250 bar, with guaiacol in the reactor feed to evaluate its impact on the formation of char and on the molecular weights of the products. The effect of residence time was investigated in the time span 1-12 min. Lignin is depolymerised during the process and guaiacol is both formed and consumed during the reaction, with clearly noticeable changes as early as in the first minute of reaction. Although the addition of guaiacol in the reactor feed causes a reduction in the weight average molecular weight of the products, the yield of char increases. Longer residence times result in repolymerisation of the reaction products as well as a further increase in the yield of monoaromatic components and char.
|
|
| 8. |
- Ahlbom, Anders, 1993
(författare)
-
Hydrothermal Depolymerisation of Kraft Lignin: The Influence of Capping Agents and Residence Time
- 2023
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Lignin, the aromatic macromolecule found in wood and other lignocellulosic biomass, is envisioned as a future renewable source of aromatic compounds that can be used as, for example, chemicals, fuel additives and resins. A way in which this can be realised is by depolymerising the lignin once it has been isolated from the lignocellulosic biomass. Hydrothermal methods that employ water as a reaction medium are suggested as ways of accomplishing this. However, reactive fragments prone to repolymerisation, indeed char formation, are formed during depolymerisation, causing operational difficulties in the process as well as yield losses of the desired components. The suggestion has been made to add chemicals, i.e. capping agents, to scavenge the reactive components in order to mitigate these issues. Careful selection of reaction parameters, such as residence time and temperature, is also crucial for the process. In this work, the depolymerisation of softwood kraft lignin has been investigated under hydrothermal conditions, with additions isopropanol, glycerol and guaiacol, to investigate their potential of functioning as capping agents. A customised batch reactor (99 ml) enabling swift heating of the reaction mixture was employed at 290-335 °C and 250 bar with low residence times (1-12 min). The result of the hydrothermal depolymerisation of lignin was an aqueous suspension with a strong smoky odour. No apparent separate liquid organic phase was formed, although a char fraction precipitated. Characterisation of the products indicated a rapid depolymerisation of the lignin, since inter-unit ether linkages were cleaved, which was later followed by a slower repolymerisation. Additions of isopropanol, glycerol and guaiacol, reduced the weight average molecular weights (Mw) of the product fractions. Only isopropanol appeared to be able to reduce the amount of char formed from the lignin. Subsequent aftertreatment of the product would be required to obtain a usable product.
|
|
| 9. |
|
|
| 10. |
|
|
