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

Abstract

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 residualmore »« less

Authors:: Shirazi, Yaser; Viamajala, Sridhar; Varanasi, Sasidhar

Publication Date:: 2020-09-10

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

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

OSTI Identifier:: 1659331

Alternate Identifier(s):: OSTI ID: 1799190

Grant/Contract Number:: EE0005993; CHE-1230609

Resource Type:: Published Article

Journal Name:: Frontiers in Chemistry

Additional Journal Information:: Journal Name: Frontiers in Chemistry Journal Volume: 8; Journal ID: ISSN 2296-2646

Publisher:: Frontiers Media SA

Country of Publication:: Switzerland

Language:: English

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

Citation Formats


                    Shirazi, Yaser, Viamajala, Sridhar, and Varanasi, Sasidhar. In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation.  Switzerland: N. p., 2020. 
Web.  doi:10.3389/fchem.2020.00786.

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                    Shirazi, Yaser, Viamajala, Sridhar, & Varanasi, Sasidhar. In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation.  Switzerland.  https://doi.org/10.3389/fchem.2020.00786

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                    Shirazi, Yaser, Viamajala, Sridhar, and Varanasi, Sasidhar. Thu .  
"In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation".  Switzerland.  https://doi.org/10.3389/fchem.2020.00786.

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@article{osti_1659331,

  title        = {In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation},

  author       = {Shirazi, Yaser and Viamajala, Sridhar and Varanasi, Sasidhar},

  abstractNote = {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.},

  doi          = {10.3389/fchem.2020.00786},

  journal      = {Frontiers in Chemistry},

  number       = ,

  volume       = 8,

  place        = {Switzerland},

  year         = {2020},

  month        = {9}

}

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

Abstract

Citation Formats

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Cultivation of Microalgae at Extreme Alkaline pH Conditions: A Novel Approach for Biofuel Production
journal, July 2017

Review and experimental study on pyrolysis and hydrothermal liquefaction of microalgae for biofuel production
journal, January 2017

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

Insight into the Deactivation and Regeneration of HZSM-5 Zeolite Catalysts in the Conversion of Dimethyl Ether to Olefins
journal, September 2018

Comparison of Lignin, Macroalgae, Wood, and Straw Fast Pyrolysis
journal, February 2013

Thermoanalytical Characterization and Catalytic Conversion of Deoiled Micro Algae and Jatropha Seed Cake
journal, August 2016

Triacylglyceride Thermal Cracking: Pathways to Cyclic Hydrocarbons
journal, December 2011

High-yield production of fuel- and oleochemical-precursors from triacylglycerols in a novel continuous-flow pyrolysis reactor
journal, October 2016

Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review
journal, September 2017

Exploiting diversity and synthetic biology for the production of algal biofuels
journal, August 2012

Catalytic pyrolysis of individual components of lignocellulosic biomass
journal, January 2014

Opportunities for simultaneous oil extraction and transesterification during biodiesel fuel production from microalgae: A review
journal, September 2016

Quantification of triglyceride content in oleaginous materials using thermo-gravimetry
journal, November 2017

Catalytic pyrolysis of microalga Chlorella pyrenoidosa for production of ethylene, propylene and butene
journal, January 2013

Comparative study of pyrolysis of algal biomass from natural lake blooms with lignocellulosic biomass
journal, December 2011

Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols
journal, January 2015

Investigation on Pyrolysis of Low Lipid Microalgae Chlorella vulgaris and Dunaliella salina
journal, November 2013

Chemical composition and protein digestibility of poultry by-product meals for salmonid diets
journal, October 1993

Role of Potassium Exchange in Catalytic Pyrolysis of Biomass over ZSM-5: Formation of Alkyl Phenols and Furans
journal, February 2017

Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system
journal, December 2014

Characterization and product formation during the catalytic and non-catalytic pyrolysis of the green microalgae Chlamydomonas reinhardtii
journal, April 2018

Study of bio-oil and bio-char production from algae by slow pyrolysis
journal, September 2013

Energy-efficient extraction of fuel from Chlorella vulgaris by ionic liquid combined with CO2 capture
journal, December 2015

Recent developments on algal biochar production and characterization
journal, December 2017

Prediction of heating values of biomass fuel from elemental composition
journal, July 2005

Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude
journal, October 2016

A review on bio-fuel production from microalgal biomass by using pyrolysis method
journal, February 2018

Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review
journal, January 2014

Review of fast pyrolysis of biomass and product upgrading
journal, March 2012

A review of thermochemical conversion of microalgal biomass for biofuels: chemistry and processes
journal, January 2017

Characterization of microalga Chlorella as a fuel and its thermogravimetric behavior
journal, February 2013

Hydrocarbons from Spirulina Pyrolysis Bio-oil Using One-Step Hydrotreating and Aqueous Extraction of Heteroatom Compounds
journal, May 2016

Investigation into the shape selectivity of zeolite catalysts for biomass conversion
journal, April 2011

Catalytic pyrolysis of microalgae for production of aromatics and ammonia
journal, January 2013

Fast pyrolysis of microalgae remnants in a fluidized bed reactor for bio-oil and biochar production
journal, January 2013

Biomass pyrolysis: a state-of-the-art review
journal, September 2008

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007

Fast pyrolysis of microalgae to produce renewable fuels
journal, June 2004

Catalytic pyrolysis of green algae for hydrocarbon production using H+ZSM-5 catalyst
journal, August 2012

Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass
journal, January 2016

Pyrolytic Fractionation: A Promising Thermochemical Technique for Processing Oleaginous (Algal) Biomass
journal, November 2017

Assessment of the effect of high ash content in pulverized coal combustion
journal, May 2007

Flash Pyrolysis of Oleaginous Biomass in a Fluidized-Bed Reactor
journal, July 2017

Non-catalytic fast pyrolysis and catalytic fast pyrolysis of Nannochloropsis oculata using Co-Mo/γ-Al2O3 catalyst for valuable chemicals
journal, September 2018

Hydroprocessing challenges in biofuels production
journal, November 2013