In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation

Shirazi, Yaser; Viamajala, Sridhar; Varanasi, Sasidhar

doi:10.3389/fchem.2020.00786

Title: In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation

Journal Article · Thu Sep 10 00:00:00 EDT 2020 · Frontiers in Chemistry

DOI:https://doi.org/10.3389/fchem.2020.00786· OSTI ID:1659331

Shirazi, Yaser; Viamajala, Sridhar; Varanasi, Sasidhar

Microalgae are attractive feedstocks for biofuel production and are especially suitable for thermochemical conversion due to the presence of thermally labile constituents—lipids, starch and protein. However, the thermal degradation of starch and proteins produces water as well as other O- and N-compounds that are mixed-in with energy-dense lipid pyrolysis products. To produce hydrocarbon-rich products from microalgae biomass, we assessed in situ and ex situ catalytic pyrolysis of a lipid-rich Chlorella sp. in the presence of the HZSM-5 zeolite catalyst over a temperature range of 450–550°C. Results show that product yields and compositions were similar under both in situ and ex situ conditions with benzene, toluene and xylene produced as the primary aromatic products. Yields of aromatics increased with increasing temperature and the highest aromatic yield (36.4% g aromatics/g ash-free microalgae) and selectivity (87% g aromatics/g bio-oil) was obtained at 550°C. Also, at this temperature, oxygenates and nitrogenous compounds were not detected among the liquid products during ex situ catalytic pyrolysis. We also assessed the feasibility of a two-step fractional pyrolysis approach integrated with vapor phase catalytic upgrading. In these experiments, the biomass was first pyrolyzed at 320°C to degrade and volatilize starch, protein and free fatty acids. Then, the residual biomass was pyrolyzed again at 450°C to recover products from triglyceride decomposition. The volatiles from each fraction were passed through an ex situ catalyst bed. Results showed that net product yields from the 2-step process were similar to the single step ex situ catalytic pyrolysis at 450°C indicating that tailored vapor phase upgrading can be applied to allow separate recovery of products from the chemically distinct biomass components—(1) lower calorific value starch and proteins and (2) energy-dense lipids.

View Journal Article

Cite

Export

Save

Research Organization:: Univ. of Toledo, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: EE0005993; CHE-1230609

OSTI ID:: 1659331

Alternate ID(s):: OSTI ID: 1799190

Journal Information:: Frontiers in Chemistry, Journal Name: Frontiers in Chemistry Vol. 8; ISSN 2296-2646

Publisher:: Frontiers Media SACopyright Statement

Country of Publication:: Switzerland

Language:: English

References (50)

A Critical View on Catalytic Pyrolysis of Biomass Venderbosch, R. H. ChemSusChem, Vol. 8, Issue 8 https://doi.org/10.1002/cssc.201500115	journal	April 2015
Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites: Catalyst screening in a pyroprobe Du, Zhenyi; Ma, Xiaochen; Li, Yun Bioresource Technology, Vol. 139 https://doi.org/10.1016/j.biortech.2013.04.053	journal	July 2013
A review of catalytic upgrading of bio-oil to engine fuels Mortensen, P. M.; Grunwaldt, J.-D.; Jensen, P. A. Applied Catalysis A: General, Vol. 407, Issue 1-2, p. 1-19 https://doi.org/10.1016/j.apcata.2011.08.046	journal	November 2011
Microalgae as biodiesel & biomass feedstocks: Review & analysis of the biochemistry, energetics & economics Williams, Peter J. le B.; Laurens, Lieve M. L. Energy & Environmental Science, Vol. 3, Issue 5 https://doi.org/10.1039/B924978H	journal	January 2010
High-Yield Production of Fatty Nitriles by One-Step Vapor-Phase Thermocatalysis of Triglycerides Shirazi, Yaser; Tafazolian, Hosein; Viamajala, Sridhar ACS Omega, Vol. 2, Issue 12 https://doi.org/10.1021/acsomega.7b01502	journal	December 2017
Cultivation of Microalgae at Extreme Alkaline pH Conditions: A Novel Approach for Biofuel Production Vadlamani, Agasteswar; Viamajala, Sridhar; Pendyala, Brahmaiah ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 8 https://doi.org/10.1021/acssuschemeng.7b01534	journal	July 2017
Review and experimental study on pyrolysis and hydrothermal liquefaction of microalgae for biofuel production Chiaramonti, David; Prussi, Matteo; Buffi, Marco Applied Energy, Vol. 185 https://doi.org/10.1016/j.apenergy.2015.12.001	journal	January 2017
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Insight into the Deactivation and Regeneration of HZSM-5 Zeolite Catalysts in the Conversion of Dimethyl Ether to Olefins Cordero-Lanzac, Tomás; Ateka, Ainara; Pérez-Uriarte, Paula Industrial & Engineering Chemistry Research, Vol. 57, Issue 41 https://doi.org/10.1021/acs.iecr.8b03308	journal	September 2018
Comparison of Lignin, Macroalgae, Wood, and Straw Fast Pyrolysis Trinh, Trung Ngoc; Jensen, Peter Arendt; Dam-Johansen, Kim Energy & Fuels, Vol. 27, Issue 3 https://doi.org/10.1021/ef301927y	journal	February 2013
Thermoanalytical Characterization and Catalytic Conversion of Deoiled Micro Algae and Jatropha Seed Cake Sebestyén, Zoltán; Barta-Rajnai, Eszter; Czégény, Zsuzsanna Energy & Fuels, Vol. 30, Issue 10 https://doi.org/10.1021/acs.energyfuels.6b01024	journal	August 2016
Triacylglyceride Thermal Cracking: Pathways to Cyclic Hydrocarbons Kubátová, Alena; Št’ávová, Jana; Seames, Wayne S. Energy & Fuels, Vol. 26, Issue 1 https://doi.org/10.1021/ef200953d	journal	December 2011
High-yield production of fuel- and oleochemical-precursors from triacylglycerols in a novel continuous-flow pyrolysis reactor Shirazi, Yaser; Viamajala, Sridhar; Varanasi, Sasidhar Applied Energy, Vol. 179 https://doi.org/10.1016/j.apenergy.2016.07.025	journal	October 2016
Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review Wang, Shurong; Dai, Gongxin; Yang, Haiping Progress in Energy and Combustion Science, Vol. 62 https://doi.org/10.1016/j.pecs.2017.05.004	journal	September 2017
Exploiting diversity and synthetic biology for the production of algal biofuels Georgianna, D. Ryan; Mayfield, Stephen P. Nature, Vol. 488, Issue 7411 https://doi.org/10.1038/nature11479	journal	August 2012
Catalytic pyrolysis of individual components of lignocellulosic biomass Wang, Kaige; Kim, Kwang Ho; Brown, Robert C. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41288A	journal	January 2014
Opportunities for simultaneous oil extraction and transesterification during biodiesel fuel production from microalgae: A review Skorupskaite, Virginija; Makareviciene, Violeta; Gumbyte, Milda Fuel Processing Technology, Vol. 150 https://doi.org/10.1016/j.fuproc.2016.05.002	journal	September 2016
Quantification of triglyceride content in oleaginous materials using thermo-gravimetry Maddi, Balakrishna; Vadlamani, Agasteswar; Viamajala, Sridhar Journal of Analytical and Applied Pyrolysis, Vol. 128 https://doi.org/10.1016/j.jaap.2017.10.006	journal	November 2017
Catalytic pyrolysis of microalga Chlorella pyrenoidosa for production of ethylene, propylene and butene Dong, Xinglong; Chen, Zhaoan; Xue, Song RSC Advances, Vol. 3, Issue 48 https://doi.org/10.1039/C3RA43850C	journal	January 2013
Comparative study of pyrolysis of algal biomass from natural lake blooms with lignocellulosic biomass Maddi, Balakrishna; Viamajala, Sridhar; Varanasi, Sasidhar Bioresource Technology, Vol. 102, Issue 23 https://doi.org/10.1016/j.biortech.2011.09.055	journal	December 2011
Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols Mukarakate, Calvin; McBrayer, Josefine D.; Evans, Tabitha J. Green Chemistry, Vol. 17, Issue 8 https://doi.org/10.1039/C5GC00805K	journal	January 2015
Investigation on Pyrolysis of Low Lipid Microalgae Chlorella vulgaris and Dunaliella salina Gong, Xun; Zhang, Biao; Zhang, Yang Energy & Fuels, Vol. 28, Issue 1 https://doi.org/10.1021/ef401500z	journal	November 2013
Chemical composition and protein digestibility of poultry by-product meals for salmonid diets Dong, Faye M.; Hardy, Ronald W.; Haard, Norman F. Aquaculture, Vol. 116, Issue 2-3 https://doi.org/10.1016/0044-8486(93)90005-J	journal	October 1993
Role of Potassium Exchange in Catalytic Pyrolysis of Biomass over ZSM-5: Formation of Alkyl Phenols and Furans Mullen, Charles A.; Tarves, Paul C.; Boateng, Akwasi A. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 3 https://doi.org/10.1021/acssuschemeng.6b02262	journal	February 2017
Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system Wang, Kaige; Johnston, Patrick A.; Brown, Robert C. Bioresource Technology, Vol. 173 https://doi.org/10.1016/j.biortech.2014.09.097	journal	December 2014
Characterization and product formation during the catalytic and non-catalytic pyrolysis of the green microalgae Chlamydomonas reinhardtii Andrade, L. A.; Batista, F. R. X.; Lira, T. S. Renewable Energy, Vol. 119 https://doi.org/10.1016/j.renene.2017.12.056	journal	April 2018
Study of bio-oil and bio-char production from algae by slow pyrolysis Chaiwong, K.; Kiatsiriroat, T.; Vorayos, N. Biomass and Bioenergy, Vol. 56 https://doi.org/10.1016/j.biombioe.2013.05.035	journal	September 2013
Energy-efficient extraction of fuel from Chlorella vulgaris by ionic liquid combined with CO2 capture Yu, Xinhai; Yang, Jie; Lu, Haitao Applied Energy, Vol. 160 https://doi.org/10.1016/j.apenergy.2015.04.074	journal	December 2015
Recent developments on algal biochar production and characterization Yu, Kai Ling; Lau, Beng Fye; Show, Pau Loke Bioresource Technology, Vol. 246 https://doi.org/10.1016/j.biortech.2017.08.009	journal	December 2017
Prediction of heating values of biomass fuel from elemental composition Friedl, A.; Padouvas, E.; Rotter, H. Analytica Chimica Acta, Vol. 544, Issue 1-2 https://doi.org/10.1016/j.aca.2005.01.041	journal	July 2005
Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude Jarvis, Jacqueline M.; Sudasinghe, Nilusha M.; Albrecht, Karl O. Fuel, Vol. 182 https://doi.org/10.1016/j.fuel.2016.05.107	journal	October 2016
A review on bio-fuel production from microalgal biomass by using pyrolysis method Azizi, Kolsoom; Keshavarz Moraveji, Mostafa; Abedini Najafabadi, Hamed Renewable and Sustainable Energy Reviews, Vol. 82 https://doi.org/10.1016/j.rser.2017.10.033	journal	February 2018
Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review Rezaei, Pouya Sirous; Shafaghat, Hoda; Daud, Wan Mohd Ashri Wan Applied Catalysis A: General, Vol. 469 https://doi.org/10.1016/j.apcata.2013.09.036	journal	January 2014
Review of fast pyrolysis of biomass and product upgrading Bridgwater, A. V. Biomass and Bioenergy, Vol. 38, p. 68-94 https://doi.org/10.1016/j.biombioe.2011.01.048	journal	March 2012
A review of thermochemical conversion of microalgal biomass for biofuels: chemistry and processes Kumar, Gopalakrishnan; Shobana, Sutha; Chen, Wei-Hsin Green Chemistry, Vol. 19, Issue 1 https://doi.org/10.1039/C6GC01937D	journal	January 2017
Characterization of microalga Chlorella as a fuel and its thermogravimetric behavior Rizzo, Andrea Maria; Prussi, Matteo; Bettucci, Lorenzo Applied Energy, Vol. 102 https://doi.org/10.1016/j.apenergy.2012.08.039	journal	February 2013
Hydrocarbons from Spirulina Pyrolysis Bio-oil Using One-Step Hydrotreating and Aqueous Extraction of Heteroatom Compounds Elkasabi, Yaseen; Chagas, Bruna M. E.; Mullen, Charles A. Energy & Fuels, Vol. 30, Issue 6 https://doi.org/10.1021/acs.energyfuels.6b00473	journal	May 2016
Investigation into the shape selectivity of zeolite catalysts for biomass conversion Jae, Jungho; Tompsett, Geoffrey A.; Foster, Andrew J. Journal of Catalysis, Vol. 279, Issue 2, p. 257-268 https://doi.org/10.1016/j.jcat.2011.01.019	journal	April 2011
Catalytic pyrolysis of microalgae for production of aromatics and ammonia Wang, Kaige; Brown, Robert C. Green Chemistry, Vol. 15, Issue 3 https://doi.org/10.1039/C3GC00031A	journal	January 2013
Fast pyrolysis of microalgae remnants in a fluidized bed reactor for bio-oil and biochar production Wang, Kaige; Brown, Robert C.; Homsy, Sally Bioresource Technology, Vol. 127 https://doi.org/10.1016/j.biortech.2012.08.016	journal	January 2013
Biomass pyrolysis: a state-of-the-art review Babu, B. V. Biofuels, Bioproducts and Biorefining, Vol. 2, Issue 5 https://doi.org/10.1002/bbb.92	journal	September 2008
Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass Huber, George W.; Corma, Avelino Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201 https://doi.org/10.1002/anie.200604504	journal	September 2007
Fast pyrolysis of microalgae to produce renewable fuels Miao, Xiaoling; Wu, Qingyu; Yang, Changyan Journal of Analytical and Applied Pyrolysis, Vol. 71, Issue 2, p. 855-863 https://doi.org/10.1016/j.jaap.2003.11.004	journal	June 2004
Catalytic pyrolysis of green algae for hydrocarbon production using H+ZSM-5 catalyst Thangalazhy-Gopakumar, Suchithra; Adhikari, Sushil; Chattanathan, Shyamsundar Ayalur Bioresource Technology, Vol. 118 https://doi.org/10.1016/j.biortech.2012.05.080	journal	August 2012
Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar Green Chemistry, Vol. 18, Issue 20 https://doi.org/10.1039/C6GC01189F	journal	January 2016
Pyrolytic Fractionation: A Promising Thermochemical Technique for Processing Oleaginous (Algal) Biomass Maddi, Balakrishna; Viamajala, Sridhar; Varanasi, Sasidhar ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 1 https://doi.org/10.1021/acssuschemeng.7b02309	journal	November 2017
Assessment of the effect of high ash content in pulverized coal combustion Jayanti, S.; Maheswaran, K.; Saravanan, V. Applied Mathematical Modelling, Vol. 31, Issue 5 https://doi.org/10.1016/j.apm.2006.03.022	journal	May 2007
Flash Pyrolysis of Oleaginous Biomass in a Fluidized-Bed Reactor Urban, Brook; Shirazi, Yaser; Maddi, Balakrishna Energy & Fuels, Vol. 31, Issue 8 https://doi.org/10.1021/acs.energyfuels.7b01306	journal	July 2017
Non-catalytic fast pyrolysis and catalytic fast pyrolysis of Nannochloropsis oculata using Co-Mo/γ-Al2O3 catalyst for valuable chemicals Gautam, Ribhu; Vinu, R. Algal Research, Vol. 34 https://doi.org/10.1016/j.algal.2018.06.024	journal	September 2018
Hydroprocessing challenges in biofuels production Furimsky, Edward Catalysis Today, Vol. 217 https://doi.org/10.1016/j.cattod.2012.11.008	journal	November 2013

Similar Records

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

Journal Article · Wed Feb 03 00:00:00 EST 2016 · Energy and Fuels · OSTI ID:1659331

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; +5 more

Biofuels from Microalgae: Review of Products, Processes and Potential, with Special Focus on Dunaliella sp.

Book · Thu Dec 31 00:00:00 EST 2009 · OSTI ID:1659331

Huesemann, Michael H; Benemann, John R

Optimization of Biomass Pyrolysis Vapor Upgrading Using a Laminar Entrained-Flow Reactor System

Journal Article · Fri Apr 24 00:00:00 EDT 2020 · Energy and Fuels · OSTI ID:1659331

Peterson, Braden; Engtrakul, Chaiwat; Evans, Tabitha J.; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Chlorella
pyrolysis
zeolite
bio-oil
biochar
biofuels
HZSM-5

Title: In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation

Citation Formats

References (50)

Similar Records

Related Subjects