Jukka Koskinen

A study on Supercritical Water Gasification of black liquor conducted in Stainless Steel and Nickel-Chromium-Molybdenum reactors.

BACKGROUND This study presents supercritical water gasification (SCWG) as an alternative treatment process for black liquor: investigating the impacts of black liquor constituents, temperature and catalyst. The preliminary experiments include SCWG of sucrose and isoeugenol in stainless steel reactor, as model compounds of sugars and lignin. Then, the experiments of SCWG of black liquor are performed in stainless steel and INCONEL 625 reactors. RESULTS The results illustrated the impacts of temperature, black liquor constituents and nickel catalyst on the SCWG process. Temperature and the INCONEL reactor promoted gasification efficiency and hot gas efficiency: over 80% hot gas efficiency was reached for black liquor in the INCONEL reactor at 700 °C. Experiments on model compounds have shown that sugars generate more carbon dioxide, while lignin generates more methane. Hydrogen fraction and yield increased with temperature; nevertheless, black liquor generated hydrogen-rich gas. The INCONEL reactor increased hot gas efficiency despite no significant impact on carbon gasification efficiency: hydrogen is promoted dramatically. In addition, temperature and the INCONEL catalyst reduce tar and char formation as well. CONCLUSIONS Supercritical water gasification (SCWG) is potentially a suitable treatment for black liquor: it has no evaporation requirement and high hot gas efficiency. This process can be a solution for non-wood mills and can increase the product spectrum of Kraft mills by operating as a parallel treatment. On the other hand, sulphur balance is to be investigated for integration with Kraft mills together with a detailed feasibility study.

Performance of biofuel processes utilising separate lignin and carbohydrate processing.

Novel biofuel pathways with increased product yields are evaluated against conventional lignocellulosic biofuel production processes: methanol or methane production via gasification and ethanol production via steam-explosion pre-treatment. The novel processes studied are ethanol production combined with methanol production by gasification, hydrocarbon fuel production with additional hydrogen produced from lignin residue gasification, methanol or methane synthesis using synthesis gas from lignin residue gasification and additional hydrogen obtained by aqueous phase reforming in synthesis gas production. The material and energy balances of the processes were calculated by Aspen flow sheet models and add on excel calculations applicable at the conceptual design stage to evaluate the pre-feasibility of the alternatives. The processes were compared using the following criteria: energy efficiency from biomass to products, primary energy efficiency, GHG reduction potential and economy (expressed as net present value: NPV). Several novel biorefinery concepts gave higher energy yields, GHG reduction potential and NPV.

Enhanced biofuel processes utilizing separate lignin and carbohydrate processing of lignocellulose

ABSTRACT Enhanced biofuel production routes utilizing separate lignin and carbohydrate processing of lignocellulose are analyzed and compared with two conventional routes; the methanol and methane production via syngas from biomass. The enhanced processes studied are: hydrocarbons production by hydrogenation of biomass based sugars by hydrogen obtained from lignin gasification, and ethanol production by biomass hydrolysis and fermentation and conversion of residual lignin into methanol via syngas. The analysis of processes was done by rigorous flowsheet modeling including power production calculations and realistic heat integration and evaluation based on energy yield, greenhouse gas (GHG) reduction and net present value (NPV). The enhanced processes via separate lignin and sugar processing can run in two modes: either being energy self-sufficient or utilizing external low temperature heat and power. The processes can operate with high efficiency as ‘waste heat and power to gas and liquids’ processes for producing liquid or gaseous fuels especially when excess energy is available e.g. in summer. Of all the processes studied the enhanced hydrocarbon production process integrated with external low temperature heat source gave the largest GHG reduction and highest NPV. External low temperature heat and electricity is converted into fuels in 136% higher heating value (116% lower heating value) efficiency.

Green chemicals from pulp production black liquor by partial wet oxidation

To reduce greenhouse gas emissions, more sustainable sources of energy, fuel and chemicals are needed. Biomass side streams such as black liquor, which is a by-product of pulp production, has the potential to be used for this purpose. The aim of the study was the production of carboxylic acids, such as lactic acid, formic acid and acetic acid, from kraft and non-wood black liquor. The processes studied were partial wet oxidation (PWO) and catalytic partial wet oxidation (CPWO). The results show that the yield of carboxylic acid is higher when treated by PWO than the results from CPWO at temperatures of 170°C and 230°C. The results shows that the PWO process can increase the yield of carboxylic acids and hydroxy acids in black liquor, reduce lignin content and decrease pH, which makes further separation of the acids more favourable. The hydroxy acids are valuable raw materials for biopolymers, and acetic acid and formic acid are commonly used chemicals conventionally produced from fossil feedstock.