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Derivatizing of Fast Pyrolysis Bio-Oil and Coprocessing in Fixed Bed Hydrotreater
RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.ORCID iD: 0000-0003-4198-6104
RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical and Pharmaceutical Toxicology.
RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.ORCID iD: 0009-0001-1523-5393
RISE Research Institutes of Sweden, Bioeconomy and Health, Chemical Process and Pharmaceutical Development.ORCID iD: 0000-0003-0137-0030
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2022 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 36, no 15, p. 8274-8287Article in journal (Refereed) Published
Abstract [en]

In several countries forest-based biofuels are being developed and to some extent also deployed. Fast pyrolysis bio-oil produced from, for example, sawdust, has now been coprocessed in fluid catalytic cracking refinery units in a number of commercial trials. However, this application is limited to about 10% of the total feed, and coprocessing in conventional fixed bed hydrotreaters is necessary to reach the high potential with this feedstock. Feeding and upgrading of fast pyrolysis bio-oil in a fixed bed reactor configuration is still problematic due to the inherent bio-oil properties. Stabilization of reactive compounds in fast pyrolysis bio-oil and mild hydrotreatment in a separate refining unit prior to refinery integration has therefore been developed the past decade. Another approach, presented here, involves complete dewatering of fast pyrolysis bio-oil by azeotropic distillation using mesityl oxide as the solvent, followed by conversion of the abundant hydroxyl compounds via mixed anhydride esterification methodology using an external source of mixed carboxylic acids of different chain lengths originating from renewable tall oil fatty acids, providing a lipophilic feed component. Dewatering and derivatizing were carried out in reactors up to 50 dm3 with a mass ratio of fast pyrolysis bio-oil to tall oil fatty acid of 10:13. The produced lipophilic oils were miscible with a petroleum light gas oil fraction and exhibited superior stability even after accelerated aging at elevated temperature (80 °C). The derivatized oils were thus mixed with light gas oil, with a proportion of 30 wt % derivatized oil in final blends and hydrotreated continuously in pilot fixed bed reactors for 14 days at 4 operating conditions without plugging or excessive exotherms. The test conditions were varied; the reactor pressure was either 55 or 80 bar, temperature 380 or 400 °C, and liquid hourly space velocity either 1 or 2 h-1 during the hydrotreatment. Successful hydrodeoxygenation and desulfurization were accomplished, whereas an increasing nitrogen concentration could be observed in the liquid products with the particular catalyst and reaction conditions employed. The observed hydrogen consumption (15-20 g/kg feed) was compared with the stoichiometric consumption for direct deoxygenation and with typical consumptions for industrial hydrotreated vegetable oil processing. The measured biogenic carbon content in hydrotreated liquid products (26.7%) agreed extremely well with the calculated biogenic carbon content in the hydrotreating feed (26.6%) that consisted of the blend of derivatized oil and petroleum light gas oil. The overall results are very promising since simple unit operations can be used to produce derivatized fast pyrolysis bio-oils that do not need additional standalone hydrotreating units but can be coprocessed in existing ones

Place, publisher, year, edition, pages
American Chemical Society , 2022. Vol. 36, no 15, p. 8274-8287
Keywords [en]
Chemical reactors, Dewatering, Distillation, Fatty acids, Gas oils, Liquids, Petroleum refining, Coprocessing, Fast pyrolysis bio-oil, Fixed bed, Fixed bed reactor, Fixed-bed reactors, Hydrotreaters, Hydrotreatment, Light gasoils, Liquid products, Tall oil fatty acids, Fluid catalytic cracking
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:ri:diva-60177DOI: 10.1021/acs.energyfuels.2c01608Scopus ID: 2-s2.0-85136171355OAI: oai:DiVA.org:ri-60177DiVA, id: diva2:1699852
Note

Funding details: Energimyndigheten, Dnr 2017-010695, P45131-1; Funding text 1: The Swedish Energy Agency through project P45131-1 (Dnr 2017-010695) is gratefully acknowledged for financial support of parts of the development work. We also thank all colleagues within RISE and Preem who have contributed with ideas and recommendations during the project work.

Available from: 2022-09-29 Created: 2022-09-29 Last updated: 2025-02-18Bibliographically approved

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Janosik, TomaszHällgren, Anne-CharlotteHedberg, MartinBernlind, Christian

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