绿色生物燃料生物丁醇分离新技术
广东省食品药品职业技术学校, 实训中心, 广东广州 510663
| 摘 要： | 随着石油资源的日益减少，生物丁醇作为一种以生物质为原料的高能量生物燃料，比生物乙醇有着更好的应用前景，是石油等化石能源的首选替代品。然而发酵液中除了丁醇外，还含有丙酮、乙醇以及绝大部分的水，分离效果差及分离成本高成为生物丁醇发展的瓶颈，为此，开发高效节能的分离技术成为生物丁醇能否产业化的关键。传统的提纯方法使发酵液先经过粗分离塔蒸馏，去掉发酵固体物和部分水，得到浓缩的有机溶剂。然后继续用蒸馏法分离物料得到乙醇、丙酮和正丁醇。针对生物丁醇发酵液体系分离困难且能耗大的问题，介绍了吸附、气提、薄膜渗透汽化、薄膜萃取等新型分离技术，尤其重点介绍盐析过程改善了发酵法生产正丁醇的传统精馏工段。通过盐析工艺除去发酵液中大部分的水分，能够极大的降低后续精馏操作的能量消耗，提供一种新的高效、节能分离方法。这些盐析剂廉价易得，容易回收循环利用，并且所使用的无机盐不会污染环境。盐析工艺适用条件温和，操作简单，不仅能节约能耗，同时能够降低CO2排放，实现节能减排。 |
| 关 键 词： | 生物丁醇; 分离; 盐析; 萃取 |
| DOI： | 10.57237/j.jest.2023.06.001 |
View:
Downloads:
收稿日期: 2023-11-23
接受日期: 2023-12-27
在线出版日期: 2023-12-28
Emerging Separation Techniques for Butanol Biofuel
Training Center, Guangdong Food and Drug Vocational Technical School, Guangzhou 510663, China
| Abstract: | Biobutanol, a high-energy biofuel made from biomass, has better application prospects than bioethanol. With the dwindling of petroleum resources, biobutanol is one of the preferred alternatives to petroleum and other fossil energy sources. However, in addition to butanol, the biobutanol fermentation broth contains acetone, ethanol and most of the water. Poor separation effect and high separation cost have become one of the bottlenecks for the development of biobutanol. Therefore, the development of efficient and energy-saving separation technology is one of the keys to the industrialization of biobutanol. The traditional purification method has the fermentation broth first distilled in a prefractionator to remove the fermentation solids and some of the water, resulting in a concentrated organic solvent. The solvent is then separated by distillation to obtain ethanol, acetone and n-butanol. Aiming at the problem of difficult and energy-consuming separation of biobutanol fermentation broth, we introduce emerging separation techniques such as adsorption, gas extraction, pervaporation, and pertraction. Particular emphasis is placed on the salting-out process which improves the traditional distillation section of biobutanol production. Removing most of the water in the fermentation broth through the salting-out process can greatly reduce the energy consumption of subsequent distillation operations, providing a new efficient and energy-saving separation method. These salting agents are cheap and easy to obtain, easy to recover and recycle, and the inorganic salt used will not pollute the environment. Salting-out process is featured with mild conditions and simple operation, not only saving energy consumption, but also reducing CO2 emissions, and realizing energy saving and emission reduction. |
| Keywords: | Biobutanol; Separation; Salting-out; Extraction |
参考文献
| [1] | DÜRRE P. Biobutanol: An attractive biofuel [M/OL] // Biotechnology Journal. 2007: 1525-1534. https://doi.org/10.1002/biot.200700168. |
| [2] | KUJAWSKA A, KUJAWSKI J, BRYJAK M, et al. ABE fermentation products recovery methods - A review [M/OL] // Renewable and Sustainable Energy Reviews. 2015: 648-661. https://doi.org/10.1016/j.rser.2015.04.028. |
| [3] | KUMAR S, CHO J H, PARK J, et al. Advances in diesel–alcohol blends and their effects on the performance and emissions of diesel engines [J/OL]. Renewable and Sustainable Energy Reviews, 2013, 22: 46-72. https://doi.org/10.1016/J.RSER.2013.01.017. |
| [4] | XIE S, ZHANG Y, YI C, et al. Biobutanol recovery from model solutions using potassium pyrophosphate [J/OL]. Journal of Chemical Technology and Biotechnology, 2017, 92(6): 1229-1235. https://doi.org/10.1002/jctb.5113. |
| [5] | XIE S, YI C, QIU X. Salting-out effect of potassium pyrophosphate (K4P2O7) on the separation of biobutanol from an aqueous solution [J/OL]. Journal of Chemical Technology and Biotechnology, 2016, 91(6): 1860-1867. https://doi.org/10.1002/jctb.4779. |
| [6] | TAO L, HE X, TAN E C D, et al. Comparative techno-economic analysis and reviews of n-butanol production from corn grain and corn stover [J/OL]. Biofuels, Bioproducts and Biorefining, 2014, 8(3): 342-361 [2022-09-05]. https://onlinelibrary.wiley.com/doi/full/10.1002/bbb.1462. |
| [7] | TAO L, TAN E C D, MCCORMICK R, et al. Techno-economic analysis and life-cycle assessment of cellulosic isobutanol and comparison with cellulosic ethanol and n-butanol [J/OL]. Biofuels, Bioproducts and Biorefining, 2014, 8(1): 30-48. https://doi.org/10.1002/bbb.1431. |
| [8] | MAITY S K. Opportunities, recent trends and challenges of integrated biorefinery: Part II [J/OL]. Renewable and Sustainable Energy Reviews, 2015, 43: 1446-1466. https://doi.org/10.1016/J.RSER.2014.08.075. |
| [9] | KUITTINEN S, HIETAHARJU J, BHATTARAI I, et al. Technoeconomic analysis and environmental sustainability estimation of bioalcohol production from barley straw [J/OL]. Biocatalysis and Agricultural Biotechnology, 2022, 43(July): 102427. https://doi.org/10.1016/j.bcab.2022.102427. |
| [10] | BANKAR S B, SURVASE S A, OJAMO H, et al. Biobutanol: The outlook of an academic and industrialist [J/OL]. RSC Advances, 2013, 3(47): 24734-24757. https://doi.org/10.1039/c3ra43011a. |
| [11] | FU C, LI Z, SONG W, et al. A new process for separating biofuel based on the salt + 1-butanol + water system [J/OL]. Fuel, 2020, 278: 118402. https://doi.org/10.1016/j.fuel.2020.118402. |
| [12] | TAN J, SUN Z, HUANG H, et al. Salting-out: A novel purification technique in biorefinery [J/OL]. Desalination, 2023, 564: 116790. https://doi.org/10.1016/J.DESAL.2023.116790. |
| [13] | SUN Z, TAN J, ZHOU G, et al. Sugaring-out plus salting-out: A novel separation and purification technique for biofuel [J/OL]. Fuel, 2024, 357: 129787 [2023-09-17]. https://linkinghub.elsevier.com/retrieve/pii/S0016236123024018. |
| [14] | STOCKHARDT J S, HULL C M. Vapor-Liquid Equilibria and Boiling-Point Composition Relations for Systems n-Butanol-Water and Isobutanol-Water [J/OL]. Industrial and Engineering Chemistry, 1931, 23(12): 1438-1440. https://doi.org/10.1021/IE50264A034. |
| [15] | HIGASHIDE W, LI Y, YANG Y, et al. Metabolic engineering of Clostridium cellulolyticum for production of isobutanol from cellulose [J/OL]. Applied and Environmental Microbiology, 2011, 77(8): 2727-2733. https://doi.org/10.1128/AEM.02454-10. |
| [16] | FU C, LI Z, ZHANG Y, et al. Assessment of extraction options for a next-generation biofuel: Recovery of bio-isobutanol from aqueous solutions [J/OL]. Engineering in Life Sciences, 2021, 21(10): 653-665 [2021-07-09]. https://onlinelibrary.wiley.com/doi/full/10.1002/elsc.202000090. |
| [17] | FU C, LI Z, JIA C, et al. Recent advances on bio-based isobutanol separation [J/OL]. Energy Conversion and Management: X, 2021, 10: 100059 [2020-12-10]. https://linkinghub.elsevier.com/retrieve/pii/S2590174520300313. |
| [18] | FU C, LI Z, SUN Z, et al. A review of salting-out effect and sugaring-out effect: Driving forces for novel liquid-liquid extraction of biofuels and biochemicals [J/OL]. Frontiers of Chemical Science and Engineering, 2020, 15: 854–871. https://doi.org/10.1007/s11705-020-1980-3. |
| [19] | YANG L, CEN P, ZHU Z. Study on acetone/butanol fermentation with in-situ solvent extraction [J]. Journal of Zhejiang University (Natural Science), 1992, 26(4): 387-398. |
| [20] | EOM M H, KIM W, LEE J, et al. Modeling of a biobutanol adsorption process for designing an extractive fermentor [J/OL]. Industrial and Engineering Chemistry Research, 2013, 52(2): 603-611. https://doi.org/10.1021/ie301249z. |
| [21] | 刘佳. 气提吸附法提取丙酮丁醇工艺的研究 [D]. 河北科技大学, 2011. |
| [22] | LUO J, YI S, SU Y, et al. Separation and concentration of butanol from acetone-butanol-ethanol mixed solution by pervaporation [J]. Chemical Engineering (China), 2010, 38(2): 43-46. |
| [23] | GROOT W J, SOEDJAK H S, DONCK P B, et al. Butanol recovery from fermentations by liquid-liquid extraction and membrane solvent extraction [J/OL]. Bioprocess Engineering, 1990, 5(5): 203-216. https://doi.org/10.1007/BF00376227. |
| [24] | WAN P K, LAN J C W, CHEN P W, et al. Recovery of intracellular ectoine from Halomonas salina cells with poly (propylene) glycol/salt aqueous biphasic system [J/OL]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 82: 28-32. https://doi.org/10.1016/j.jtice.2017.11.003. |
| [25] | HATTI-KAUL R. Aqueous two-phase systems: A general overview [J/OL]. Applied Biochemistry and Biotechnology - Part B Molecular Biotechnology, 2001, 19(3): 269-277. http://dx.doi.org/10.1016/B978-0-08-088504-9.00124-0. |
| [26] | DAI J Y, SUN Y Q, XIU Z L. Separation of bio-based chemicals from fermentation broths by salting-out extraction [J/OL]. Engineering in Life Sciences, 2014, 14(2): 108-117. https://doi.org/10.1002/elsc.201200210. |
| [27] | DAI J Y, LIU C J, XIU Z L. Sugaring-out extraction of 2,3-butanediol from fermentation broths [J/OL]. Process Biochemistry, 2015, 50(11): 1951-1957. https://doi.org/10.1016/j.procbio.2015.08.004. |
| [28] | FU H, WANG X, SUN Y, et al. Effects of salting-out and salting-out extraction on the separation of butyric acid [J/OL]. Separation and Purification Technology, 2017, 180: 44-50. https://doi.org/10.1016/j.seppur.2017.02.042. |
| [29] | XIE S, JIA C, WANG Z, et. al. Mechanistic Insight into Selective Deoxygenation of l -Lysine to Produce Biobased Amines [J/OL]. ACS Sustainable Chemistry & Engineering, 2020, 8(31): 11805-11817. DOI: 10.1021/acssuschemeng.0c04052. |
| [30] | XIE S, SONG W, FU C, et al. Separation of acetone: From a water miscible system to an efficient aqueous two-phase system [J/OL]. Separation and Purification Technology, 2018, 192: 55-61. https://doi.org/10.1016/j.seppur.2017.09.056. |
| [31] | YI C, ZHANG Y, XIE S, et al. Salting-out extraction of bio-based isobutanol from an aqueous solution [J/OL]. Journal of Chemical Technology and Biotechnology, 2018, 93(2): 372-384. https://doi.org/10.1002/jctb.5365. |
| [32] | XIE S, ZHANG Y, ZHOU Y, et al. Salting-out of bio-based 2,3-butanediol from aqueous solutions [M/OL]//Journal of Chemical Technology and Biotechnology. 2017: 122-132. https://doi.org/10.1002/jctb.4999. |
| [33] | XIE S, QIU X, JI W, et al. Salting-out of 1,3-propanediol from aqueous solutions by inorganic electrolytes [J/OL]. Journal of Chemical Technology & Biotechnology, 2016, 91(11): 2793-2801. https://doi.org/10.1002/JCTB.4886. |
| [34] | SUN J, RAO B, ZHANG L, et al. Extraction of Acetoin From Fermentation Broth Using an Acetone/Phosphate Aqueous Two-Phase System [J/OL]. Chemical Engineering Communications, 2012, 199(11): 1492-1503. https://doi.org/10.1080/00986445.2012.683901. |
| [35] | GROSS P M. The “salting out” of non-electrolytes from aqueous solutions [J/OL]. Chemical Reviews, 1933, 13(1): 91-101. https://doi.org/10.1021/cr60044a007. |
| [36] | XIE S, LI Z, ZHU G. Salting-out Effect on the Separation and Purification of Acetic Esters: Salting-out Agents, Theory, and Applications [J/OL]. Separation and Purification Reviews, 2022 [2023-06-12]. https://www.tandfonline.com/doi/abs/10.1080/15422119.2022.2159837. |
| [37] | MATKOVICH C E, CHRISTIAN G D. Salting-Out of Acetone from Water-Basis of a New Solvent Extraction System [J/OL]. Analytical Chemistry, 1973, 45(11): 1915-1921. https://doi.org/10.1021/ac60333a023. |
| [38] | FU H, YANG S T, XIU Z. Phase separation in a salting-out extraction system of ethanol-ammonium sulfate [J/OL]. Separation and Purification Technology, 2015, 148: 32-37. https://doi.org/10.1016/j.seppur.2015.04.042. |
| [39] | LYKLEMA J. Simple Hofmeister series [J/OL]. Chemical Physics Letters, 2009, 467(4-6): 217-222. https://doi.org/10.1016/j.cplett.2008.11.013. |
| [40] | LI F, LI Q, WU S, et al. Salting-out extraction of allicin from garlic (Allium sativum L.) based on ethanol/ammonium sulfate in laboratory and pilot scale [J/OL]. Food Chemistry, 2017, 217: 91-97. https://doi.org/10.1016/J.FOODCHEM.2016.08.092. |
| [41] | MALINOWSKI J J, DAUGULIS A J. Salt effects in extraction of ethanol, 1‐butanol and acetone from aqueous solutions [J/OL]. AIChE Journal, 1994, 40(9): 1459-1465. https://doi.org/10.1002/aic.690400905. |
| [42] | AYDOǦAN Ö, BAYRAKTAR E, MEHMETOǦLU Ü. Aqueous two-phase extraction of lactic acid: Optimization by response surface methodology [J/OL]. Separation Science and Technology, 2011, 46(7): 1164-1171. https://doi.org/10.1080/01496395.2010.550270. |
| [43] | WU H S, WANG Y J. Salting-out effect on recovery of 1,3-propanediol from fermentation broth [J/OL]. Industrial and Engineering Chemistry Research, 2012, 51(33): 10930-10935. https://doi.org/10.1021/ie300404t. |
| [44] | FU C, XIE S. Salts and 1-propanol induced aqueous two-phase systems: phase separation and application [J/OL]. Journal of Chemical Technology and Biotechnology, 2019, 94(7): 2372-2381. https://doi.org/10.1002/jctb.6036. |
| [45] | FU C, SONG W, YI C, et al. Creating efficient novel aqueous two-phase systems: Salting-out effect and high solubility of salt [J/OL]. Fluid Phase Equilibria, 2019, 490: 77-85. https://doi.org/10.1016/j.fluid.2019.03.002. |
| [46] | RAZMARA R S, DANESHFAR A, SAHRAI R. Determination of methylene blue and sunset yellow in wastewater and food samples using salting-out assisted liquid–liquid extraction [J/OL]. Journal of Industrial and Engineering Chemistry, 2011, 17(3): 533-536. https://doi.org/10.1016/J.JIEC.2010.10.028. |
| [47] | CAI Y, CAI Y, SHI Y, et al. A liquid-liquid extraction technique for phthalate esters with water-soluble organic solvents by adding inorganic salts [J/OL]. Microchimica Acta, 2007, 157(1-2): 73-79 [2023-11-24]. https://link.springer.com/article/10.1007/s00604-006-0625-7. |
| [48] | HU M, ZHAI Q, LIU Z, et al. Liquid-Liquid and Solid-Liquid Equilibrium of the Ternary System Ethanol + Cesium Sulfate + Water at (10, 30, and 50)°C [J/OL]. Journal of Chemical and Engineering Data, 2003, 48(6): 1561-1564 [2023-11-24]. https://pubs.acs.org/doi/full/10.1021/je0301803. |
| [49] | GUO W, MA J, WANG Y, et al. Liquid-liquid equilibrium of aqueous two-phase systems composed of hydrophilic alcohols (ethanol/2-propanol/1-propanol) and MgSO 4/ZnSO 4 at (303.15 and 313.15) K and correlation [J/OL]. Thermochimica Acta, 2012, 546: 8-15. http://dx.doi.org/10.1016/j.tca.2012.07.022. |
| [50] | 韩晓丽. 正丁醇生产新工艺 [J]. 辽宁化工, 1998(4): 44-46. |
| [51] | CARD J, FARRELL L. Separation of alcohol-water mixtures using salts [J/OL]. 1982 [2023-11-24]. https://www.osti.gov/biblio/5250443. |
| [52] | 许文友. 碳酸钾分离乙醇-丙酮-丁醇-水体系 [J]. 过程工程学报, 2001, 1(3): 318-320. |
| [53] | 许文有. 用氟化钾分离乙醇－丙酮－丁醇－水体系的研究[J]. 石油化工, 1996(01): 32-34. |
| [54] | HU B L, QIU X Q, YANG D J. Separation of butanol-acetone-water system using repulsive extraction [J]. Huanan Ligong Daxue Xuebao/Journal of South China University of Technology (Natural Science), 2003, 31(12): 58. |
| [55] | XIE S, YI C, QIU X. Energy-saving recovery of acetone, butanol, and ethanol from a prefractionator by the salting-out method [J/OL]. Journal of Chemical and Engineering Data, 2013, 58(11): 3297-3303. https://doi.org/10.1021/je400740z. |
| [56] | XIE S, QIU X, YI C. Separation of a Biofuel: Recovery of Biobutanol by Salting-Out and Distillation [J/OL]. Chemical Engineering and Technology, 2015, 38(12): 2181-2188. https://doi.org/10.1002/ceat.201500140. |
| [57] | XIE S, SONG W, YI C, et al. Salting-out extraction systems of ethanol and water induced by high-solubility inorganic electrolytes [J/OL]. Journal of Industrial and Engineering Chemistry, 2017, 56: 145-150. https://doi.org/10.1016/j.jiec.2017.07.006. |
| [58] | HAN X. Improvement on Conventional Production of Butanol [J]. liaoning chemical industry, 1998, 04: 44-46. |
| [59] | CEN P, TSAO G T. Recent advances in the simultaneous bioreaction and product separation processes [J/OL]. Separations Technology, 1993, 3(2): 58-75. https://doi.org/10.1016/0956-9618(93)80006-D. |
| [60] | GROVER P K, RYALL R L. Critical appraisal of salting-out and its implications for chemical and biological sciences [J/OL]. Chemical Reviews, 2005, 105(1): 1-10. https://doi.org/10.1021/cr030454p. |
| [61] | YI C, XIE S, QIU X. Salting-out effect of dipotassium hydrogen phosphate on the recovery of acetone, butanol, and ethanol from a prefractionator [J/OL]. Journal of Chemical and Engineering Data, 2014, 59(5): 1507-1514. https://doi.org/10.1021/je401060m. |
| [62] | BUCHER D, KUYUCAK S. Polarization of water in the first hydration shell of K+ and Ca2+ ions [J/OL]. Journal of Physical Chemistry B, 2008, 112(35): 10786-10790. https://doi.org/10.1021/jp804694u. |
| [63] | XIE S, QIU X, YI C. Salting-out effect of tripotassium phosphate on the liquid-liquid equilibria of the (water+acetone+1-butanol+ethanol) system and the salting-out recovery [J/OL]. Fluid Phase Equilibria, 2015, 386: 7-12. https://doi.org/10.1016/j.fluid.2014.11.013. |
| [64] | XIE S, YI C, QIU X. Salting-out of acetone, 1-butanol, and ethanol from dilute aqueous solutions [J/OL]. AIChE Journal, 2015, 61(10): 3470-3478. https://doi.org/10.1002/aic.14872. |
| [65] | XIE S, JI W, ZHANG Y, et al. Biobutanol recovery from model solutions/fermentation broth using tripotassium phosphate [J/OL]. Biochemical Engineering Journal, 2016, 115: 85-92. https://doi.org/10.1016/j.bej.2016.08.010. |
