Abstract
This contribution describes an algal fractionation scheme based on cell lysing and carbohydrate hydrolysis under acidic conditions, coupled with solvent extraction, that produces algal lipids, carbohydrates, and proteinaceous solid from partially dewatered algal biomass. A design of experiments analysis was employed to identify the effect of fractionation conditions on the yields of the three product streams. By selection of appropriate conditions, the process can be steered from simple lipid extraction to near complete fractionation of the biomass. Lipid purification and upgrading were respectively achieved with a low-cost adsorbent and an inexpensive Ni-based catalyst that deoxygenated the lipids via decarboxylation/decarbonylation, an approach offering several advantages over the hydrodeoxygenation-based processes typically employed to convert lipids to hydrocarbons. The proteinaceous solids obtained were found to have much lower ash content as well as higher protein content relative to the untreated algae, enhancing the suitability of this material as a feedstock for the production of bioplastics.
Similar content being viewed by others
Data availability
The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Holttinen H, Milligan M, Ela E, Menemenlis N, Dobschinski J, Rawn B, Bessa RJ, Flynn D, LazaroEG, Detlefsen N (2013) In Methodologies to determine operating reserves due to increased wind power, Power and Energy Society General Meeting (PES), 2013 IEEE, IEEE. pp 1-10
Hirth L, Ueckerdt F, Edenhofer O (2015) Integration costs revisited–an economic framework for wind and solar variability. Renew Energy 74:925–939. https://doi.org/10.1016/j.renene.2014.08.065
Crocker M, Groppo J, Kesner S, Mohler D, Pace R, Santillan-Jimenez E, Wilson M, Schambach J, Stewart J, Zeller A (2017) A microalgae-based platform for the beneficial re-use of carbon dioxide emissions from power plants. Final Technical Report, U.S. DoE, #DE-FE0026396
Wilson MH, Groppo J, Placido A, Graham S, Morton SA, Santillan-Jimenez E, Shea A, Crocker M, Crofcheck C, Andrews R (2014) CO2 recycling using microalgae for the production of fuels. Appl Petrochem Res 4:41–53
Zhang X, Wilson K, Lee AF (2016) Heterogeneously catalyzed hydrothermal processing of C5–C6 sugars. Chem Rev 116:12328–12368. https://doi.org/10.1021/acs.chemrev.6b00311
Santillan-Jimenez E, Pace R, Marques S, Morgan T, McKelphin C, Mobley J, Crocker M (2016) Extraction, characterization, purification and catalytic upgrading of algae lipids to fuel-like hydrocarbons. Fuel 180:668–678. https://doi.org/10.1016/j.fuel.2016.04.079
Loe R, Santillan-Jimenez E, Morgan T, Sewell L, Ji Y, Jones S, Isaacs MA, Lee AF, Crocker M (2016) Effect of Cu and Sn promotion on the catalytic deoxygenation of model and algal lipids to fuel-like hydrocarbons over supported Ni catalysts. Appl Catal B Environ 191:147–156. https://doi.org/10.1016/j.apcatb.2016.03.025
Santillan-Jimenez E, Loe R, Garrett M, Morgan T, Crocker M (2018) Effect of Cu promotion on cracking and methanation during the Ni-catalyzed deoxygenation of waste lipids and hemp seed oil to fuel-like hydrocarbons. Catal Today 302:261–271. https://doi.org/10.1016/j.cattod.2017.03.025
Choubert G, Heinrich O (1993) Carotenoid pigments of the green alga Haematococcus pluvialis: assay on rainbow trout, Oncorhynchus mykiss, pigmentation in comparison with synthetic astaxanthin and canthaxanthin. Aquaculture 112:217–226. https://doi.org/10.1016/0044-8486(93)90447-7
Chen Y, Wu Y, Hua D, Li C, Harold MP, Wang J, Yang M (2015) Thermochemical conversion of low-lipid microalgae for the production of liquid fuels: challenges and opportunities. RSC Adv 5:18673–18701. https://doi.org/10.1039/C4RA13359E
Vardon DR, Sharma BK, Blazina GV, Rajagopalan K, Strathmann TJ (2012) Thermochemical conversion of raw and defatted algal biomass via hydrothermal liquefaction and slow pyrolysis. Bioresour Technol 109:178–187. https://doi.org/10.1016/j.biortech.2012.01.008
Santillan-Jimenez E, Pace R, Morgan T, Behnke C, Sajkowski DJ, Lappas A, Crocker M (2019) Co-processing of hydrothermal liquefaction algal bio-oil and petroleum feedstock to fuel-like hydrocarbons via fluid catalytic cracking. Fuel Process Technol 188:164–171. https://doi.org/10.1016/j.fuproc.2019.02.018
Zhao C, Brück T, Lercher JA (2013) Catalytic deoxygenation of microalgae oil to green hydrocarbons. Green Chem 15:1720–1739. https://doi.org/10.1039/C3GC40558C
Nelson DR, Viamajala S (2016) One-pot synthesis and recovery of fatty acid methyl esters (FAMEs) from microalgae biomass. Catal Today 269:29–39. https://doi.org/10.1016/j.cattod.2015.11.048
Laurens LM, Quinn M, Van Wychen S, Templeton DW, Wolfrum EJ (2012) Accurate and reliable quantification of total microalgal fuel potential as fatty acid methyl esters by in situ transesterification. Anal Bioanal Chem 403:167–178
Beckstrom BD, Wilson MH, Crocker M, Quinn JC (2020) Bioplastic feedstock production from microalgae with fuel co-products: a techno-economic and life cycle impact assessment. Algal Res 46:101769. https://doi.org/10.1016/j.algal.2019.101769
Chew KW, Yap JY, Show PL, Suan NH, Juan JC, Ling TC, Lee D, Chang L (2017) Microalgae biorefinery: high value products perspectives. Bioresour Technol 229:53–62
Morgan T, Santillan-Jimenez E, Huff K, Javed KR, Crocker M (2017) Use of dual detection in the gas chromatographic analysis of oleaginous biomass feeds and biofuel products to enable accurate simulated distillation and lipid profiling. Energy Fuel 31:9498–9506. https://doi.org/10.1021/acs.energyfuels.7b01445
Pegallapati AK, Frank ED (2016) Energy use and greenhouse gas emissions from an algae fractionation process for producing renewable diesel. Algal Res 18:235–240. https://doi.org/10.1016/j.algal.2016.06.019
Laurens L, Nagle N, Davis R, Sweeney N, Van Wychen S, Lowell A, Pienkos P (2015) Acid-catalyzed algal biomass pretreatment for integrated lipid and carbohydrate-based biofuels production. Green Chem 17:1145–1158. https://doi.org/10.1039/C4GC01612B
Czartoski TJ, Perkins R, Villanueva JL, Richards G (2010) Algae biomass fractionation. U.S. Patent 2010/0233761 A1
Rana MS, Ancheyta J, Sahoo SK, Rayo P (2014) Carbon and metal deposition during the hydroprocessing of Maya crude oil. Catal Today 220-222:97–105. https://doi.org/10.1016/j.cattod.2013.09.030
Santillan-Jimenez E, Crocker M (2012) Catalytic deoxygenation of fatty acids and their derivatives to hydrocarbon fuels via decarboxylation/decarbonylation. J Chem Technol Biotechnol 87:1041–1050. https://doi.org/10.1002/jctb.3775
Shi F, Wang P, Duan Y, Link D, Morreale B (2012) Recent developments in the production of liquid fuels via catalytic conversion of microalgae: experiments and simulations. RSC Adv 2:9727–9747. https://doi.org/10.1039/C2RA21594B
Mohler D, Wilson MH, Kesner S, Schambach JY, Vaughan D, Frazar M, Stewart J, Groppo J, Pace R, Crocker M (2019) Beneficial re-use of industrial CO2 emissions using microalgae: demonstration assessment and biomass characterization. Bioresour Technol 293:122014. https://doi.org/10.1016/j.biortech.2019.122014
Silva GC, Qian D, Pace R, Heintz O, Caboche G, Santillan-Jimenez E, Crocker M (2020) Promotional effect of Cu, Fe and Pt on the performance of Ni/Al2O3 in the deoxygenation of used cooking oil to fuel-like hydrocarbons. Catalysts 10:91. https://doi.org/10.3390/catal10010091
Wilson MH, Mohler DT, Groppo JG, Grubbs T, Kesner S, Frazar EM, Shea A, Crofcheck C, Crocker M (2016) Capture and recycle of industrial CO2 emissions using microalgae. Appl Petrochem Res 6:279–293. https://doi.org/10.1007/s13203-016-0162-1
Mohler DT, Wilson MH, Fan Z, Groppo JG, Crocker M (2019) Beneficial reuse of industrial CO2 emissions using a microalgae photobioreactor: waste heat utilization assessment. Energies 12:2634. https://doi.org/10.3390/en12132634
Loe R, Lavoignat Y, Maier M, Abdallah M, Morgan T, Qian D, Pace R, Santillan-Jimenez E, Crocker M (2019) Continuous catalytic deoxygenation of waste free fatty acid-based feeds to fuel-like hydrocarbons over a supported Ni-Cu catalyst. Catalysts 9:123. https://doi.org/10.3390/catal9020123
Lourenço SO, Barbarino E, Lavín PL, Lanfer Marquez UM, Aidar E (2004) Distribution of intracellular nitrogen in marine microalgae: calculation of new nitrogen-to-protein conversion factors. Eur J Phycol 39:17–32. https://doi.org/10.1080/0967026032000157156
Templeton DW, Quinn M, Van Wychen S, Hyman D, Laurens LM (2012) Separation and quantification of microalgal carbohydrates. J Chromatogr A 1270:225–234. https://doi.org/10.1016/j.chroma.2012.10.034
Jones SB, Zhu Y, Anderson DB, Hallen RT, Elliott DC, Schmidt AJ, Albrecht KO, Hart TR, Butcher MG, Drennan C (2014) Process design and economics for the conversion of algal biomass to hydrocarbons: whole algae hydrothermal liquefaction and upgrading. U.S. DOE Technical Report #PNNL-23227. https://www.pnnl.gov/main/publications/external/technical_reports/PNNL-23227.pdf. Accessed Oct 2020
Laurens LM, Chen-Glasser M, McMillan JD (2017) A perspective on renewable bioenergy from photosynthetic algae as feedstock for biofuels and bioproducts. Algal Res 24:261–264. https://doi.org/10.1016/j.algal.2017.04.002
Laurens L (2017) State of technology review-algae bioenergy. IAE Bioenergy. https://www.ieabioenergy.com/publications/state-of-technology-review-algae-bioenergy/. Accessed Oct 2020
Huo YX, Cho KM, Rivera JGL, Monte E, Shen CR, Yan Y, Liao JC (2011) Conversion of proteins into biofuels by engineering nitrogen flux. Nat Biotechnol 29:346–351. https://doi.org/10.1038/nbt.1789
Davis R, Fishman D, Frank ED, Wigmosta MS, Aden A, Coleman AM, Pienkos PT, Skaggs RJ, Venteris ER, Wang MQ (2012) Renewable diesel from algal lipids: an integrated baseline for cost, emissions, and resource potential from a harmonized model. National Renewable Energy Lab Technical Report NREL/TP-5100-55431, PNNL-21437. https://www.nrel.gov/docs/fy12osti/55431.pdf. Accessed Oct 2020
Zeller MA, Hunt R, Jones A, Sharma S (2013) Bioplastics and their thermoplastic blends from Spirulina and Chlorella microalgae. J Appl Polym Sci 130:3263–3275. https://doi.org/10.1002/app.39559
Wang K, Mandal A, Ayton E, Hunt R, Zeller M, Sharma S (2017) Modification of protein rich algal-biomass to form bioplastics and odor removal. In: Dhillon DS (ed) Protein byproducts. Elsevier, Amsterdam, pp 107–117
Beckstrom BD (2019) Bioplastic production from microalgae with fuel co-products: a techno-economic and life-cycle assessment. Thesis, Colorado State University
Dong T, Knoshaug EP, Davis R, Laurens LM, Van Wychen S, Pienkos PT, Nagle N (2016) Combined algal processing: a novel integrated biorefinery process to produce algal biofuels and bioproducts. Algal Res 19:316–323. https://doi.org/10.1016/j.algal.2015.12.021
Dong T, Van Wychen S, Nagle N, Pienkos PT, Laurens LM (2016) Impact of biochemical composition on susceptibility of algal biomass to acid-catalyzed pretreatment for sugar and lipid recovery. Algal Res 18:69–77. https://doi.org/10.1016/j.algal.2016.06.004
Nguyen TT, Lam MK, Uemura Y, Mansor N, Lim JW, Show PL, Tan IS, Lim S (2020) High biodiesel yield from wet microalgae paste via in-situ transesterification: effect of reaction parameters towards the selectivity of fatty acid esters. Fuel 272:117718. https://doi.org/10.1016/j.fuel.2020.117718
Choudhary TV, Phillips CB (2011) Renewable fuels via catalytic hydrodeoxygenation. Appl Catal A Gen 397:1–12. https://doi.org/10.1016/j.apcata.2011.02.025
Rozmysłowicz B, Maki-Arvela P, Tokarev A, Leino AR, Eränen K, Murzin DY (2012) Influence of hydrogen in catalytic deoxygenation of fatty acids and their derivatives over Pd/C. Ind Eng Chem Res 51:8922–8927. https://doi.org/10.1021/ie202421x
Peng B, Zhao C, Kasakov S, Foraita S, Lercher JA (2013) Manipulating catalytic pathways: deoxygenation of palmitic acid on multifunctional catalysts. Chem Eur J 19:4732–4741. https://doi.org/10.1002/chem.201203110
Acknowledgments
The authors thank Prof. Seth DeBolt for carbohydrate analysis. The United States Department of Energy (award no. DE-FE0029623) is thanked for financial support.
Funding
Funding was provided by the United States Department of Energy (award no. DE-FE0029623).
Author information
Authors and Affiliations
Contributions
Conceptualization: Robert Pace, Mark Crocker; formal analysis and investigation: Robert Pace, Stephanie Kesner, Tonya Morgan, Molly Frazar, Vincent Kelly; writing: Robert Pace, Eduardo Santillan-Jimenez; writing—review and editing: Robert Pace, Eduardo Santillan-Jimenez, Mark Crocker, M. Ashton Zeller; funding acquisition: Mark Crocker; resources: Mark Crocker; supervision: Mark Crocker.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Disclaimer
This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
Code availability
Not applicable.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 109 kb)
Rights and permissions
About this article
Cite this article
Pace, R., Kesner, S., Santillan-Jimenez, E. et al. Evaluation of near-ambient algal biomass fractionation conditions for bioproduct development. Biomass Conv. Bioref. 13, 131–140 (2023). https://doi.org/10.1007/s13399-020-01090-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13399-020-01090-5