Activity of water in pyrolysis oil—Experiments and modelling

Ille, Yannik; Kröhl, Fabian; Velez, Alexis; Funke, Axel; Pereda, Selva; Schaber, Karlheinz; Dahmen, Nicolaus

doi:10.1016/j.jaap.2018.08.027

Cited by 21 publications

(26 citation statements)

References 33 publications

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“…A search of the relevant literature yielded some studies, in which a surrogate composition for bio-oil or a fraction of bio-oil has been proposed. − Ille et al used experimental vapor liquid equilibrium data for the development of suitable surrogate mixtures by studying about 200 possibly suited components to represent the heavy fraction of the bio-oil, which typically condense at around 80–90 °C. Dependent upon the choice of the surrogate mixture, their results differed more than 100%, which demonstrates the importance of a carefully chosen surrogate.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic and Physical Property Estimation of Compounds Derived from the Fast Pyrolysis of Lignocellulosic Materials

et al. 2021

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The development of biomass pyrolysis oil refineries is a very promising path for the production of biofuels and bioproducts from lignocellulosic materials. Given that bio-oil is a complex mixture of organic compounds, the production of valuable bioproducts may imply the use of different separation processes, such as distillation, selective condensation, crystallization based on melting points, liquid−liquid extraction or adsorption, and/or upgrading treatments, such as catalytic cracking or hydrodeoxygenation. In this context, the main objectives of this work are (1) to propose a simple but representative composition of the bio-oil, which can be used as a bio-oil surrogate, and (2) to determine selected thermodynamic, physical, and molecular properties of the organic compounds included in the bio-oil surrogate using different estimation methods and calculation procedures. These properties are critical temperature, critical pressure, critical volume, normal boiling point, enthalpy of vaporization, vapor pressure curves, normal melting point, enthalpy of fusion, heat capacities of gas, liquid, and solid, gas and liquid standard enthalpy of formation, gas standard Gibbs free energy of formation, Hansen solubility parameters, molecular volume, and molecular diameter. This group of properties has been selected for their possible application in the simulation or design of thermochemical, separation, and upgrading processes. Additionally, the suitability of the estimated thermodynamic properties and the proposed surrogate composition has been assessed by comparing experimental and literature data with the apparent enthalpy of formation of the bio-oil predicted from the weight-averaged contributions of the compounds as well as the heat required for the pyrolysis process at 500 °C.

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Section: Introductionmentioning

confidence: 99%

Thermodynamic and Physical Property Estimation of Compounds Derived from the Fast Pyrolysis of Lignocellulosic Materials

et al. 2021

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“…Another issue in improving models for energetic evaluation of the process are condensation models, especially to better describe light volatiles that could potentially be diverted to the gaseous product stream (and, in turn, be combusted to yield more heat) instead of being recovered with the AC. While modeling of vapor liquid equilibria of FPBO is not straightforward and an ideal behavior of the water as a main component cannot be assumed, 35 including feasible models for the aqueous fractions appears to be a reasonable next step.…”

Section: Further Activitiesmentioning

confidence: 99%

Fast Pyrolysis of Wheat Straw—Improvements of Operational Stability in 10 Years of Bioliq Pilot Plant Operation

et al. 2021

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The bioliq process developed at the Karlsruhe Institute of Technology (KIT) aims at the conversion of lignocellulosic biomass into synthetic biofuels and chemicals. The process follows a two-stage concept combining decentralized pretreatment of biomass via fast pyrolysis and centralized large-scale gasification and synthesis. The process was specifically designed to convert ash-rich biomass residues, such as wheat straw, requiring special design features at least in the upstream processes. The 2 MW fast pyrolysis pilot plant at KIT was operated with wheat straw from 2009 to 2018 and since then with miscanthus. A substantial increase from less than 5 tons of wheat straw converted per test run in 2012 to more than 50 tons in 2018 was achieved. In total, up to 2018, more than 260 tons of wheat straw were converted to pyrolysis products within a total of 500 h of steady operation. Representative results of the product yields and properties were presented for test campaigns from 2015 to 2018 and compared to a process demonstration unit of the same design but with a downscale factor of 50 (10 kg/h). Mass yields from both plants are in good agreement and consistent with literature data. Experience from longer-term operation and major technical modifications made to improve the operational stability of the plant are described.

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“…Projected depletion and rising carbon footprint associated with the use of fossil resources coupled with rising energy demands have sparked the production of fuels and chemicals from biomass. , Several thermal and biochemical processes have been developed to valorize biomass residues as carbon-neutral resources. ,, Fast pyrolysis to convert lignocellulosic biomass into bio-based energy and chemicals has gained significant attention, due to its advantages of processing many types of biomass feedstocks into energy-dense liquid and solid intermediates for further energetic or chemical use. ,− Fast pyrolysis decomposes lignocellulosic biomass at temperatures of around 500 °C in an inert environment to produce fast pyrolysis bio-oil (FPBO), char (containing inorganics), and non-condensable gases, each of which can be used for fuel and chemical applications. ,,− By pyrolysis, up to 75 wt % initial dry biomass can be converted into FPBO. , FPBO is a complex product as a mixture of numerous compounds that include organic acids, ketones, aldehydes, alcohols, furans, phenols, hydro-sugars, and other oxygenates as well as water. ,,− Due to its complex nature, FPBO may be separated into various fractions to tailor its quality for specific applications . Methods employed for the fractionation of FPBO include but are not limited to centrifugation, extraction, liquid chromatography, molecular distillation, and fractional condensation. ,, Centrifugation, extraction, and liquid chromatography, although proven to be effective in separating FPBO, are expensive and impractical at industrial scales. ,,, Molecular distillation is discouraged as oxygenated compounds in FPBO become highly reactive during heating and may polymerize into coke (solid carbonaceous residue). ,,,,, …”

Section: Introductionmentioning

confidence: 99%

“…A relevant challenge met when modeling fast pyrolysis, including the condensation of fast pyrolysis volatiles, is the physicochemical characterization of the compounds found in the model. ,, Westerhof et al demonstrated this when they predicted the effects of condensation conditions on fractions of light compounds using a simple equilibrium stage model. Westerhof et al also previously compared an equilibrium flash condensation model with experimental results when they studied the control of the water content in FPBO.…”

Section: Introductionmentioning

confidence: 99%

Using Fractional Condensation to Optimize Aqueous Pyrolysis Condensates for Downstream Microbial Conversion

Parku

Krutof

Funke

et al. 2023

Ind. Eng. Chem. Res.

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This study investigated the use of fractional condensation, following the fast pyrolysis of three different ashrich biomass feedstocks, to optimize the composition of aqueous pyrolysis condensates (ACs) for downstream microbial conversion. Optimum conditions were first predicted and established theoretically by means of vapor−liquid equilibrium flash calculations that employed the modified UNIFAC Dortmund (UNIFAC-DMD) model. Thereafter, theoretical models were experimentally validated on a 10 kg/h fast pyrolysis setup. Model predictions revealed that a temperature combination of 120 and 50 °C on the first and second staged condensers, respectively, returned optimum production of AC yield and substrates at the expense of inhibitors. Satisfactory agreement existed between most experimental data and model predictions, and the qualitative trend was mostly reproduced correctly. Some noteworthy deviations were, however, observed, most especially for inhibitory compounds, which were blamed on the limitation of the UNIFAC-DMD model in accurately predicting the phase behavior of organic compounds at such very low concentrations as well as the scarcity of precise vapor pressure data for some of these organic compounds. Nonetheless, the study demonstrated how valuable theoretical phase equilibrium models are in predicting the composition of fast pyrolysis bio-oils and how fractional condensation proves to be a key upstream pre-treatment for valorizing ACs.

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Activity of water in pyrolysis oil—Experiments and modelling

Cited by 21 publications

References 33 publications

Thermodynamic and Physical Property Estimation of Compounds Derived from the Fast Pyrolysis of Lignocellulosic Materials

Thermodynamic and Physical Property Estimation of Compounds Derived from the Fast Pyrolysis of Lignocellulosic Materials

Fast Pyrolysis of Wheat Straw—Improvements of Operational Stability in 10 Years of Bioliq Pilot Plant Operation

Using Fractional Condensation to Optimize Aqueous Pyrolysis Condensates for Downstream Microbial Conversion

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