LIGNIN HYDROTHERMAL LIQUEFACTION IN SUBCRITICAL WATER TO PRODUCE BIOFUEL AND CHEMICALS
Doctoral thesis, 2018

Lignin is one of the most abundant amorphous macromolecules found in nature. Along with cellulose and hemicellulose, it forms a main component of biomass, and is mainly responsible for providing strength, rigidity and resistance to degradation. From a chemistry perspective, lignin is an important source of aromatics. In the kraft process, lignin is recovered in the form of “black liquor”, which is considered a low-value by-product. Nowadays, energy efficiency measures in the pulp and paper industry have improved to a level of having an energy surplus in the mill, making it is possible to add value to the black liquor, which represents the surplus energy, in various ways. One scenario is to extract lignin from the black liquor, which has become technically feasible by developing LignoBoost technology, and then converting the lignin into high-value products, such as specialty chemicals or bio-fuel.

In this work, hydrothermal liquefaction (HTL) of LignoBoost kraft lignin has been carried out in a small pilot plant, using sub-critical water as the medium, ZrO2, K2CO3/Na2CO3 and/or KOH/NaOH as the catalytic system, methanol as the co-solvent and phenol as the capping agent to suppress repolymerisation (e.g. formation of char). With the aim of developing the HTL process, different investigations were carried out to study the influence of methanol, the pH (8.9-10.4) through the use of different concentrations of potassium hydroxide and the use of phenol as the capping agent (2-10%); different fractions of sodium in alkali (Na/(Na+K) from 0.0-1.0) were also investigated. The reactions were performed in a fixed-bed reactor (500 cm3) at 350°C with the exception of the methanol investigation, where it was varied between 280 and 350°C, and a pressure of 25 MPa. The reactor outlet was comprised mainly of two liquid phases: one aqueous and one oil.

The pH and methanol investigations showed different results in terms of operability and yields. The yields of bio-oil, WSO and char were affected by different levels of pH and concentrations of methanol. In addition, the use of methanol led to operational difficulties due to the extensive formation of solids. For the phenol and sodium/potassium investigations, the overall yield was not affected considerably either by different phenol concentrations (2-10%) or sodium fractions in the alkali. It was possible to lower the phenol concentration in the feed to 2% and maintain fairly constant overall yields. In the case of the sodium series, it was shown that it was also possible to replace the potassium ion in the feed with the sodium ion without it having a strong effect on the product yield. This HTL process gave the same major individual compounds such as guaiacol, anisole, catechol and alkylphenols, in all of the investigations undertaken, with different trends and influences being observed depending on the parameters studied.

Biomass valorisation

base depolymerisation

biofuel

lignin

green chemicals.

Hall KA, Kemigården 4, Chalmers
Opponent: Professor Jalel Labidi, University of the Basque Country, Spain

Author

Tallal Belkheiri

Chalmers, Chemistry and Chemical Engineering, Chemical Technology

Kraft Lignin Depolymerization in Near-Critical Water: Effect of Changing Co-Solvent

Cellulose Chemistry and Technology,; Vol. 48(2014)p. 813-818

Journal article

Effect of pH on Kraft Lignin Depolymerisation in Subcritical Water

Energy & Fuels,; Vol. 30(2016)p. 4916-4924

Journal article

Hydrothermal liquefaction of kraft lignin in sub-critical water: Influence of phenol as capping agent. Tallal Belkheiri, Sven-Ingvar Andersson, Cecilia Mattsson, Lars Olausson, Hans Theliander and Lennart Vamling. Energy & Fuels (submitted).

Hydrothermal liquefaction of kraft lignin in sub-critical water: Influence of the sodium and potassium fraction. Tallal Belkheiri, Sven-Ingvar Andersson, Cecilia Mattsson, Lars Olausson, Hans Theliander and Lennart Vamling. Biomass Conversion and Biorefinery (Accepted).

Areas of Advance

Energy

Subject Categories

Chemical Process Engineering

Other Chemical Engineering

Bioenergy

ISBN

978-91-7597-703-4

Doktorsavhandlingar vid Chalmers tekniska högskola. Ny serie: 4384

Publisher

Chalmers

Hall KA, Kemigården 4, Chalmers

Opponent: Professor Jalel Labidi, University of the Basque Country, Spain

More information

Latest update

11/15/2018