Chemical properties and characterization methods for hydrothermal liquefaction bio-crude from microalgae: a review

doi:10.11949/j.issn.0438-1157.20151582

Abstract

Abstract:

Hydrothermal liquefaction (HTL) bio-crude from microalgae cannot be directly used as transportation fuels due to poor quality. A new approach for its application is integration of it and modern petroleum processing industry. The chemical properties of HTL bio-crude, including chemical composition, functional groups and heteroatom compounds constitution are summarized in this paper. The characterization methods including GC-MS, FTIR, NMR, FT-ICR MS were compared and analyzed. Formation mechanism and upgrading of HTL bio-crude were also briefly reviewed. The focus is on higher oxygenated and nitrogenous compounds content in HTL bio-crude, higher aromaticity and unsaturation degree comparing with heavy crude oil or residue oil. Catalytic hydrotreating could effectively remove heteroatom and increase hydrocarbon content. The development of microalgae-based bio-fuels depends on not only the progress in upgrading technique but also the improvement of characterization methods.

Key words: bio-crude, microalgae, hydrothermal liquefaction, functional group, heteroatom

摘要：

微藻水热液化生物油由于性质较差,不能直接作为车载燃料使用,与现代石油炼制工艺结合是一种新的应用途径。综述了微藻生物油的化学性质,包括化学组成、官能团组成与杂原子化合物组成等信息,比较分析了GC-MS、FTIR、NMR和FT-ICR MS等表征方法的异同,简要回顾了微藻水热液化反应机理和精制方法。重点指出微藻水热液化生物油中含氧、含氮化合物含量较高,并具有较高的芳香度和不饱和度,催化加氢精制能够有效脱除杂原子,并增加烷烃含量。微藻基生物燃料的发展,不仅需要精制工艺的提升,也有赖于表征方法的进步。

关键词: 生物油, 微藻, 水热液化, 官能团, 杂原子

CLC Number:

ZHANG Jixiang, JIANG Baohui, WANG Dong, WEI Yaodong. Chemical properties and characterization methods for hydrothermal liquefaction bio-crude from microalgae: a review[J]. CIESC Journal, 2016, 67(5): 1644-1653.

张冀翔, 蒋宝辉, 王东, 魏耀东. 微藻水热液化生物油化学性质与表征方法综述[J]. 化工学报, 2016, 67(5): 1644-1653.

References 54

[1]	ELLIOTT D, BECKMAN D, BRIDGWATER A V, et al. Developments in direct thermochemical liquefaction of biomass: 1983—1990 [J]. Energy & Fuels, 1991, 5(3): 399-410. DOI: 10.1021/ef00027a008.
[2]	TOOR S S, ROSENDAHL L, RUDOLF A. Hydrothermal liquefaction of biomass: a review of subcritical water technologies [J]. Energy, 2011, 36(5): 2328-2342. DOI: 10.1016/j.energy.2011.03.013.
[3]	ZHU Y H, ALBRECHT K O, ELLIOTT D C, et al. Development of hydrothermal liquefaction and upgrading technologies for lipid-extracted algae conversion to liquid fuels [J]. Algal Research-Biomass Biofuels and Bioproducts, 2013, 2(4): 455-464. DOI: 10.1016/j.algal.2013.07.003.
[4]	CHENG J, HUANG R, Yu T, et al. Biodiesel production from lipids in wet microalgae with microwave irradiation and bio-crude production from algal residue through hydrothermal liquefaction [J]. Bioresource Technology, 2014, 151: 415-418. DOI: 10.1016/j. biortech. 2013.10.033.
[5]	BRENNAN L, OWENDE P. Biofuels from microalgae—a review of technologies for production, processing, and extractions of biofuels and co-products [J]. Renewable & Sustainable Energy Reviews, 2010, 14(2): 557-577. DOI: 10.1016/j.rser.2009.10.009.
[6]	DUAN P G, SAVAGE P E. Hydrothermal liquefaction of a microalga with heterogeneous catalysts [J]. Industrial & Engineering Chemistry Research, 2011, 50(1): 52-61. DOI: 10.1021/ie100758s.
[7]	DUAN P G, SAVAGE P E. Upgrading of crude algal bio-oil in supercritical water [J]. Bioresource Technology, 2011, 102(2): 1899-1906. DOI: 10.1016/j.biortech.2010.08.013.
[8]	AKHTAR J, AMIN N A S. A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass [J]. Renewable & Sustainable Energy Reviews, 2011, 15(3): 1615-1624. DOI: 10.1016/j.rser.2010.11.054.
[9]	YEH T M, DICKINSON J G, FRANCK A, et al. Hydrothermal catalytic production of fuels and chemicals from aquatic biomass [J]. Journal of Chemical Technology and Biotechnology, 2013, 88(1): 13-24. DOI: 10.1002/jctb.3933.
[10]	PAVLOVIC I, KNEZ Z, SKERGET M. Hydrothermal reactions of agricultural and food processing wastes in sub-and supercritical water: a review of fundamentals, mechanisms, and state of research [J]. Journal of Agricultural and Food Chemistry, 2013, 61(34): 8003-8025. DOI: 10.1021/jf401008a.
[11]	XIU S N, SHAHBAZI A. Bio-oil production and upgrading research: a review [J]. Renewable & Sustainable Energy Reviews, 2012, 16(7): 4406-4414. DOI: 10.1016/j.rser.2012.04.028.
[12]	陈裕鹏, 黄艳琴, 阴秀丽, 等. 藻类生物质水热液化制备生物油的研究进展 [J]. 石油学报(石油加工), 2014, 30(4): 756-763. DOI: 10.3969/j.issn.1001-8719.2014. 04.028. CHEN Y P, HUANG Y Q, YIN X L, et al. Research progress of producing bio-oil from hydrothermal liquefaction of algae[J].Acta Petrolei Sinica (Petroleum Processing Section), 2014, 30(4): 756-763. DOI: 10.3969/j.issn.1001-8719.2014.04.028.
[13]	丁冉冉, 吴玉龙, 陈宇, 等. 藻类液化生物油的催化脱氧改质进展 [J]. 化工学报, 2014, 65(7): 2685-2695. DOI: 10.3969/j.issn.0438-1157. 2014.07.028. DING R R, WU Y L, CHEN Y, et al. Recent advances on catalytic deoxygenation upgrading of liquefaction microalgae bio-oil [J]. CIESC Journal, 2014, 65(7): 2685-2695. DOI: 10.3969/j.issn. 0438-1157.2014.07.028.
[14]	胡见波, 杜泽学, 闵恩泽. 生物质水热液化机理研究进展 [J]. 石油炼制与化工, 2012, 43(4): 87-92. HU J B, DU Z X, MIN E Z. Progress in research of reaction mechanism concering hydrothermal liquefaction of biomass [J]. Petroleum Processing and Petrochemicals, 2012, 43(4): 87-92.
[15]	PETERSON A A, VOGEL F, LACHANCE R P, et al. Thermochemical biofuel production in hydrothermal media: a review of sub-and supercritical water technologies [J]. Energy & Environmental Science, 2008, 1(1): 32-65. DOI: 10.1039/b810100k.
[16]	HUBER G W, IBORRA S, CORMA A. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering [J]. Chemical Reviews, 2006, 106(9): 4044-4098. DOI: 10.1021/cr068360d.
[17]	TRAN N H, BARTLETT J R, KANNANGARA G S K, et al. Catalytic upgrading of biorefinery oil from micro-algae [J]. Fuel, 2010, 89(2): 265-274. DOI: 10.1016/j.fuel.2009.08.015.
[18]	GUO Y, YEH T, SONG W H, et al. A review of bio-oil production from hydrothermal liquefaction of algae [J]. Renewable & Sustainable Energy Reviews, 2015, 48: 776-790. DOI: 10.1016/j.rser.2015.04.049.
[19]	TEKIN K, KARAGOZ S, BEKTAS S. A review of hydrothermal biomass processing [J]. Renewable & Sustainable Energy Reviews, 2014, 40:673-687. DOI: 10.1016/j.rser.2014.07.216.
[20]	阎立峰, 朱清时. 以生物质为原材料的化学化工 [J]. 化工学报, 2004, 55(12): 1938-1943. YAN L F, ZHU Q S. New chemical industry based on biomass [J]. Journal of Chemical Industry and Engineering (China), 2004, 55(12): 1938-1943.
[21]	OFEMIA K S, ZHANG Y, FUNK T. Hydrothermal processing of swine manure into oil using a continuous reactor system: development and testing [J]. Transactions of the Asabe, 2006, 49(2): 533-541.
[22]	LI H, LIU Z D, ZHANG Y H, et al. Conversion efficiency and oil quality of low-lipid high-protein and high-lipid low-protein microalgae via hydrothermal liquefaction [J]. Bioresource Technology, 2014, 154: 322-329. DOI: 10.1016/j.biortech.2013.12.074.
[23]	GAI C, ZHANG Y H, CHEN W T, et al. An investigation of reaction pathways of hydrothermal liquefaction using Chlorella pyrenoidosa and Spirulina platensis [J]. Energy Conversion and Management, 2015, 96: 330-339. DOI: 10.1016/j.enconman.2015.02.056.
[24]	JENA U, DAS K C, KASTNER J R. Effect of operating conditions of thermochemical liquefaction on biocrude production from Spirulina platensis [J]. Bioresource Technology, 2011, 102(10): 6221-6229. DOI: 10.1016/j.biortech.2011.02.057.
[25]	TIAN C Y, LIU Z D, ZHANG Y H, et al. Hydrothermal liquefaction of harvested high-ash low-lipid algal biomass from Dianchi Lake: effects of operational parameters and relations of products [J]. Bioresource Technology, 2015, 184: 336-343. DOI: 10.1016/j.biortech. 2014.10.093.
[26]	TOMMASO G, CHEN W T, LI P, et al. Chemical characterization and anaerobic biodegradability of hydrothermal liquefaction aqueous products from mixed-culture wastewater algae [J]. Bioresource Technology, 2015, 178: 139-146. DOI: 10.1016/j.biortech. 2014.10.011.
[27]	BILLER P, ROSS A B. Potential yields and properties of oil from the hydrothermal liquefaction of microalgae with different biochemical content [J]. Bioresource Technology, 2011, 102(1):215-225. DOI: 10.1016/j.biortech.2010.06.028.
[28]	TORRI C, ALBA L G, SAMORI C, et al. Hydrothermal treatment (HTT) of microalgae: detailed molecular characterization of HTT oil in view of HTT mechanism elucidation [J]. Energy & Fuels, 2012, 26(1): 658-671. DOI: 10.1021/ef201417e.
[29]	CHEN W T, ZHANG Y H, ZHANG J X, et al. Co-liquefaction of swine manure and mixed-culture algal biomass from a wastewater treatment system to produce bio-crude oil [J]. Applied Energy, 2014, 128: 209-216. DOI: 10.1016/j.apenergy.2014.04.068.
[30]	ZHANG J X, CHEN W T, ZHANG P, et al. Hydrothermal liquefaction of Chlorella pyrenoidosa in sub-and supercritical ethanol with heterogeneous catalysts [J]. Bioresource Technology, 2013, 133: 389-397. DOI:10.1016/j.biortech.2013.01.076.
[31]	BAI X J, DUAN P G, XU Y P, et al. Hydrothermal catalytic processing of pretreated algal oil: a catalyst screening study [J]. Fuel, 2014, 120: 141-149. DOI:10.1016/j.fuel.2013.12.012.
[32]	DUAN P G, SAVAGE P E. Catalytic hydrotreatment of crude algal bio-oil in supercritical water [J]. Applied Catalysis B-Environmental, 2011, 104(1/2): 136-143. DOI: 10.1016/j.apcatb.2011.02.020.
[33]	VARDON D R, SHARMA B K, SCOTT J, et al. Chemical properties of biocrude oil from the hydrothermal liquefaction of Spirulina algae, swine manure, and digested anaerobic sludge [J]. Bioresource Technology, 2011, 102(17): 8295-8303. DOI: 10.1016/j.biortech. 2011.06.041.
[34]	GAI C, ZHANG Y H, CHEN W T, et al. Energy and nutrient recovery efficiencies in biocrude oil produced via hydrothermal liquefaction of Chlorella pyrenoidosa [J]. RSC Advances, 2014, 4(33): 16958-16967. DOI: 10.1039/c3ra46607h.
[35]	ZOU S P, WU Y L, YANG M D, et al. Production and characterization of bio-oil from hydrothermal liquefaction of microalgae Dunaliella tertiolecta cake [J]. Energy, 2010, 35(12): 5406-5411. DOI: 10.1016/j.energy.2010.07.013.
[36]	ROSS A B, BILLER P, KUBACKI M L, et al. Hydrothermal processing of microalgae using alkali and organic acids [J]. Fuel, 2010, 89(9): 2234-2243. DOI: 10.1016/j.fuel.2010.01.025.
[37]	LEONARDIS I, CHIABERGE S, FIORANI T, et al. Characterization of bio-oil from hydrothermal liquefaction of organic waste by NMR spectroscopy and FTICR mass spectrometry [J]. ChemSusChem, 2013, 6(1): 160-167. DOI: 10.1002/cssc.201200314.
[38]	XU D H, SAVAGE P E. Characterization of biocrudes recovered with and without solvent after hydrothermal liquefaction of algae [J]. Algal Research-Biomass Biofuels and Bioproducts, 2014, 6: 1-7. DOI: 10.1016/j.algal.2014.08.007.
[39]	AUDO M, PARASCHIV M, QUEFFELEC C, et al. Subcritical hydrothermal liquefaction of microalgae residues as a green route to alternative road binders [J]. ACS Sustainable Chemistry & Engineering, 2015, 3(4): 583-590. DOI: 10.1021/acssuschemeng. 5b00088.
[40]	VARDON D R, SHARMA B K, BLAZINA G V, et al. Thermochemical conversion of raw and defatted algal biomass via hydrothermal liquefaction and slow pyrolysis [J]. Bioresource Technology, 2012, 109: 178-187. DOI: 10.1016/j.biortech. 2012.01.008.
[41]	史权, 赵锁奇, 徐春明, 等. 傅立叶变换离子回旋共振质谱仪在石油组成分析中的应用 [J]. 质谱学报, 2008, 29(6): 367-378. SHI Q, ZHAO S Q, XU C M, et al. Fourier transform ion cyclotron resonance mass spectrometry and its application in petroleum analysis [J]. Journal of Chinese Mass Spectrometry Society, 2008, 29(6): 367-378.
[42]	CHIABERGE S, LEONARDIS I, FIORANI T, et al. Bio-oil from waste: a comprehensive analytical study by soft-ionization FTICR mass spectrometry [J]. Energy & Fuels, 2014, 28(3): 2019-2026. DOI: 10. 1021/ef402452f.
[43]	SUDASINGHE N, DUNGAN B, LAMMERS P, et al. High resolution FT-ICR mass spectral analysis of bio-oil and residual water soluble organics produced by hydrothermal liquefaction of the marine microalga Nannochloropsis salina [J]. Fuel, 2014, 119:47-56. DOI: 10.1016/j.fuel.2013.11.019.
[44]	SUDASINGHE N, REDDY H, CSAKAN N, et al. Temperature-dependent lipid conversion and nonlipid composition of microalgal hydrothermal liquefaction oils monitored by Fourier transform ion cyclotron resonance mass spectrometry [J]. BioEnergy Research, 2015: 1-11. DOI: 10.1007/s12155-015-9635-9.
[45]	SANGUINETI M M, HOURANI N, WITT M, et al. Analysis of impact of temperature and saltwater on Nannochloropsis salina bio-oil production by ultra high resolution APCI FT-ICR MS [J]. Algal Research, 2015, 9: 227-235. DOI: 10.1016/j.algal.2015.02.026.
[46]	MINOWA T, YOKOYAMA S, KISHIMOTO M, et al. Oil production from algal cells of Dunaliella tertiolecta by direct thermochemical liquefaction [J]. Fuel, 1995, 74(12): 1735-1738. DOI: 10.1016/0016-2361(95)80001-X.
[47]	JENA U, DAS K C, KASTNER J R. Comparison of the effects of Na2CO3, Ca3(PO4)2, and NiO catalysts on the thermochemical liquefaction of microalga Spirulina platensis [J]. Applied Energy, 2012, 98: 368-375. DOI: 10.1016/j.apenergy.2012.03.056.
[48]	BILLER P, RILEY R, ROSS A B. Catalytic hydrothermal processing of microalgae: decomposition and upgrading of lipids [J]. Bioresource Technology, 2011, 102(7): 4841-4848. DOI: 10.1016/j.biortech. 2010.12.113.
[49]	XU Y F, ZHENG X J, YU H Q, et al. Hydrothermal liquefaction of Chlorella pyrenoidosa for bio-oil production over Ce/HZSM-5 [J]. Bioresource Technology, 2014, 156: 1-5. DOI: 10.1016/j.biortech. 2014.01.010.
[50]	DUAN P G, BAI X J, XU Y P, et al. Catalytic upgrading of crude algal oil using platinum/gamma alumina in supercritical water [J]. Fuel, 2013, 109: 225-233. DOI:10.1016/j.fuel.2012.12.074.
[51]	ELLIOTT D C, HART T R, SCHMIDT A J, et al. Process development for hydrothermal liquefaction of algae feedstocks in a continuous-flow reactor [J]. Algal Research-Biomass Biofuels and Bioproducts, 2013, 2(4): 445-454. DOI: 10.1016/j.algal.2013.08.005.
[52]	ROUSSIS S G, CRANFORD R, SYTKOVETSKIY N. Thermal treatment of crude algae oils prepared under hydrothermal extraction conditions [J]. Energy & Fuels, 2012, 26(8): 5294-5299. DOI: 10.1021/ef300798b.
[53]	DUAN P G, WANG B, XU Y P. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae [J]. Bioresource Technology, 2015, 186: 58-66. DOI: 10.1016/j.biortech.2015.03.050.
[54]	SUDASINGHE N, CORT J R, HALLEN R, et al. Hydrothermal liquefaction oil and hydrotreated product from pine feedstock characterized by heteronuclear two-dimensional NMR spectroscopy and FT-ICR mass spectrometry [J]. Fuel, 2014, 137: 60-69. DOI: 10.1016/j.fuel.2014.07.069.