Research status and development trend of high-value utilization of crude glycerol

doi:10.16085/j.issn.1000-6613.2019-1634

Abstract

Abstract:

Crude glycerol is the by-product of the biodiesel production, and its green treatment and application have become an urgent research topic. This paper introduces the research status of biological, chemical and electrochemical conversion methods of crude glycerol. On this basis, the research status of the production of 1,3-propanediol and hydrogen from crude glycerol by bioconversion, the production of acrolein and polyurethane by chemical conversion and the preparation of fuel cell by electrochemical conversion are reviewed, respectively. The research and development trend of high-value use of crude glycerol are also analyzed. Crude glycerol bioconversion has the disadvantages of the high cost of the culture medium and difficulty in product separation, which limits the current industrial application. Meanwhile, chemical conversion methods are still in the initial research stage, whereas electrochemical conversion methods have a good development space as emerging technologies. This paper points out that crude glycerol can be used as a new type of biomass resource, and the research of crude glycerol-based chemicals and new materials have broad prospects for development.

Key words: crude glycerol, high-value utilization, bioconversion, chemical conversion, electrochemical conversion

摘要：

粗甘油是生物柴油生产过程的副产品，对其进行绿色处理和应用已成为迫切研究的课题。本文分类介绍了粗甘油生物、化学和电化学转化方法的研究现状。在此基础上分别对粗甘油通过生物转化方式生产1,3-丙二醇、氢气等化学品，利用化学转化方式生产丙烯醛和聚氨酯高分子材料和电化学转化方式制备燃料电池的研究现状进行了综述，并分析了粗甘油高值化利用研究及发展趋势。粗甘油生物转化存在培养基成本较高、产物分离困难等不足，限制了目前的工业化应用；化学转化方式还处于初期研究阶段；电化学转化方式作为新兴技术，具有良好的发展空间。本文指出粗甘油可以作为一种新型的生物质资源，粗甘油基化学品与新材料的开发研究具有广阔的发展前景。

关键词: 粗甘油, 高值化利用, 生物转化, 化学转化, 电化学转化

CLC Number:

S216

Dongxiang WANG, Chen WANG, Shijie WANG, Guizhuan XU, Chun CHANG. Research status and development trend of high-value utilization of crude glycerol[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3041-3048.

王冬祥, 王晨, 王世杰, 徐桂转, 常春. 粗甘油高值化利用研究现状及发展趋势[J]. 化工进展, 2020, 39(8): 3041-3048.

References

1	修志龙, 郭峰, 梁志霞, 等. 第二代生物柴油及其生物炼制关键技术[J]. 化工进展, 2010, 29(S1): 58-63.
1	XIU Z L, GUO F, LIANG Z X, et, al. Key technologies of second-generation biodiesel and its biorefinery[J]. Chemical Industry and Engineering Progress, 2010, 29(S1): 58-63.
2	AHMAD T, DANISH M, KALE P, et al. Optimization of process variables for biodiesel production by transesterification of flaxseed oil and produced biodiesel characterizations[J]. Renewable Energy, 2019, 139: 1272-1280.
3	TABATABAEI M, AGHBASHLO M, DEHHAGHI M, et al. Reactor technologies for biodiesel production and processing: a review[J]. Progress in Energy and Combustion Science, 2019, 74: 239-303.
4	VERAS S, ROJAS P, FLORENCIO L, et al. Production of 1,3-propanediol from pure and crude glycerol using a UASB reactor with attached biomass in silicone support[J]. Bioresour. Technol., 2019, 279: 140-148.
5	熊犍, 宋炜, 叶君. 降低生物柴油生产成本的研究进展[J]. 化工进展, 2007, 26(6): 774-777.
5	XIONG J, SONG Y, YE J. Research development in reducing production cost of biodiesel[J]. Chemical Industry and Engineering Progress, 2007, 26(6): 774-777.
6	KUMAR L R, YELLAPU S K, TYAGI R D, et al. A review on variation in crude glycerol composition, bio-valorization of crude and purified glycerol as carbon source for lipid production[J]. Bioresource Technology, 2019, 293: 122155.
7	SUN Y, ZHENG Y, WANG X, et al. Fermentation performance and mechanism of a novel microbial consortium DUT08 for 1,3-propandiol production from biodiesel-derived crude glycerol under non-strictly anaerobic conditions[J]. Process Biochemistry, 2019, 83: 27-34.
8	CHOL C G, DHABHAI R, DALAI A K, et al. Purification of crude glycerol derived from biodiesel production process: experimental studies and techno-economic analyses[J]. Fuel Processing Technology, 2018, 178: 78-87.
9	ANITHA M, KAMARUDIN S K, KOFLI N T. The potential of glycerol as a value-added commodity[J]. Chemical Engineering Journal, 2016, 295: 119-130.
10	YANG X, CHOI H S, LEE J H, et al. Improved production of 1,3-propanediol from biodiesel-derived crude glycerol by Klebsiella pneumoniae in fed-batch fermentation[J]. Chemical Engineering Journal, 2018, 349: 25-36.
11	ZAHEDI S, SOLERA R, GARCíA-MORALES J L, et al. Effect of the addition of glycerol on hydrogen production from industrial municipal solid waste[J]. Fuel, 2016, 180: 343-347.
12	SZYMANOWSKA-POWA?OWSKA D. 1,3-Propanediol production from crude glycerol by Clostridium butyricum DSP1 in repeated batch[J]. Electronic Journal of Biotechnology, 2014, 17(6): 322-328.
13	PARATE R, MANE R, DHARNE M, et al. Mixed bacterial culture mediated direct conversion of bio-glycerol to diols[J]. Bioresource Technology, 2018, 250: 86-93.
14	刘海军, 徐友海, 张代佳, 等. 两步发酵法生产1,3-丙二醇的研究[J]. 食品与发酵工业, 2006(2): 4-7.
14	LIU H J, XU Y H, ZHANG D J, et al. Investigation of two successive bioprocesses for the microbial production of 1,3-propanediol[J]. Food and Fermentation Industries, 2006(2): 4-7.
15	SILVA G P DA, MACK M, CONTIERO J. Glycerol: a promising and abundant carbon source for industrial microbiology[J]. Biotechnology Advances, 2009, 27(1): 30-39.
16	朱春杰, 方柏山. 微生物转化法生产1,3-丙二醇的研究进展[J]. 华侨大学学报(自然科学版), 2009, 30(5): 481-486.
16	ZHU C J, FANG B S. Progress on the production of 1,3-propanediol by microbial conversion[J]. Journal of Huaqiao University (Natural Science), 2009, 30(5): 481-486.
17	VIVEK N, CHRISTOPHER M, KUMAR M K, et al. Pentose rich acid pretreated liquor as co-substrate for 1,3-propanediol production[J]. Renewable Energy, 2018, 129: 794-799.
18	VIVEK N, PANDEY A, BINOD P. Biological valorization of pure and crude glycerol into 1,3-propanediol using a novel isolate Lactobacillus brevis N1E9.3.3[J]. Bioresource Technology, 2016, 213: 222-230.
19	熊玮. 丁酸梭菌1,3-丙二醇的过程模型化和优化[D]. 厦门: 厦门大学, 2012.
19	XIONG W. Process modeling and optimization of Clostridium butyricum 1,3-propanediol[D]. Xiamen: Xiamen University, 2012.
20	SILVA F M S, OLIVEIRA L B, MAHLER C F, et al. Hydrogen production through anaerobic co-digestion of food waste and crude glycerol at mesophilic conditions[J]. International Journal of Hydrogen Energy, 2017, 42(36): 22720-22729.
21	PACHAPUR V L, SARMA S J, BRAR S K, et al. Surfactant mediated enhanced glycerol uptake and hydrogen production from biodiesel waste using co-culture of Enterobacter aerogenes and Clostridium butyricum[J]. Renewable Energy, 2016, 95: 542-551.
22	FABER M D O, FERREIRA-LEIT?O V S. Optimization of biohydrogen yield produced by bacterial consortia using residual glycerin from biodiesel production[J]. Bioresource Technology, 2016, 219: 365-370.
23	POTT R W M, HOWE C J, DENNIS J S. Photofermentation of crude glycerol from biodiesel using Rhodopseudomonas palustris: comparison with organic acids and the identification of inhibitory compounds[J]. Bioresource Technology, 2013, 130: 725-730.
24	ZHANG D, XIAO N, MAHBUBANI K T, et al. Bioprocess modelling of biohydrogen production by Rhodopseudomonas palustris: model development and effects of operating conditions on hydrogen yield and glycerol conversion efficiency[J]. Chemical Engineering Science, 2015, 130: 68-78.
25	SENGMEE D, CHEIRSILP B, SUKSAROGE T T, et al. Biophotolysis-based hydrogen and lipid production by oleaginous microalgae using crude glycerol as exogenous carbon source[J]. International Journal of Hydrogen Energy, 2017, 42(4): 1970-1976.
26	吴梦佳. 污泥混合菌种暗发酵与光发酵联合制氢[D]. 天津: 天津大学, 2014.
26	WU M J. Bio-hydrogen production from a combined process of dark and photo fermentation by mixed bacteria from anaerobic sludge[D]. Tianjin: Tianjin University, 2014.
27	CHOOKAEW T, O-THONG S, PRASERTSAN P. Biohydrogen production from crude glycerol by two stage of dark and photo fermentation[J]. International Journal of Hydrogen Energy, 2015, 40(24): 7433-7438.
28	SARMA S J, BRAR S K, LE BIHAN Y, et al. Bio-hydrogen production by biodiesel-derived crude glycerol bioconversion: a techno-economic evaluation[J]. Bioprocess and Biosystems Engineering, 2013, 36(1): 1-10.
29	LI J, LIU R, CHANG G, et al. A strategy for the highly efficient production of docosahexaenoic acid by Aurantiochytrium limacinum SR21 using glucose and glycerol as the mixed carbon sources[J]. Bioresource Technology, 2015, 177: 51-57.
30	LI X, LIU J, CHEN G, et al. Extraction and purification of eicosapentaenoic acid and docosahexaenoic acid from microalgae: a critical review[J]. Algal Research, 2019, 43: 101619.
31	LUNG Y, TAN C H, SHOW P L, et al. Docosahexaenoic acid production from crude glycerol by Schizochytrium limacinum SR21[J]. Clean Technologies and Environmental Policy, 2016, 18(7): 2209-2216.
32	CHEN W, ZHOU P, ZHANG M, et al. Transcriptome analysis reveals that up-regulation of the fatty acid synthase gene promotes the accumulation of docosahexaenoic acid in Schizochytrium sp. S056 when glycerol is used[J]. Algal Research, 2016, 15: 83-92.
33	HEJNA A, KIRPLUKS M, KOSMELA P, et al. The influence of crude glycerol and castor oil-based polyol on the structure and performance of rigid polyurethane-polyisocyanurate foams[J]. Industrial Crops and Products, 2017, 95: 113-125.
34	GóMEZ E F, LUO X, LI C, et al. Biodegradability of crude glycerol-based polyurethane foams during composting, anaerobic digestion and soil incubation[J]. Polymer Degradation and Stability, 2014, 102: 195-203.
35	KOSMELA P, HEJNA A, FORMELA K, et al. The study on application of biopolyols obtained by cellulose biomass liquefaction performed with crude glycerol for the synthesis of rigid polyurethane foams[J]. Journal of Polymers and the Environment, 2018, 26(6): 2546-2554.
36	GAMA N V, SOARES B, FREIRE C S, et al. Effect of unrefined crude glycerol composition on the properties of polyurethane foams[J]. Journal of Cellular Plastics, 2017, 54(3): 633-649.
37	HU S, LI Y. Polyols and polyurethane foams from base-catalyzed liquefaction of lignocellulosic biomass by crude glycerol: effects of crude glycerol impurities[J]. Industrial Crops and Products, 2014, 57: 188-194.
38	戚小各, 何玉远, 常春, 等. 基于生物柴油副产物粗甘油的聚氨酯硬泡的制备[J]. 聚氨酯工业, 2018, 33(1): 27-30.
38	QI X G, HE Y Y, CHANG C, et al. Preparation of bio-based polyurethane foam based on crude glycerol from biodiesel[J]. Polyurethane Industry, 2018, 33(1): 27-30.
39	QI X, ZHANG Y, CHANG C, et al. Thermal, mechanical, and morphological properties of rigid crude glycerol‐based polyurethane foams reinforced with nanoclay and microcrystalline cellulose[J]. European Journal of Lipid Science and Technology, 2018, 120(5): 1700413.
40	刘利威, 常春, 戚小各, 等. 粗甘油生物基聚氨酯泡沫的改性研究[J]. 高校化学工程学报, 2019, 33(2): 469-474.
40	LIU L W, CHANG C, QI X G, et al. Modification of crude glycerol bio-based polyurethane foams[J]. Journal of Chemical Engineering of Chinese Universities, 2019, 33(2): 469-474.
41	JUTRZENKA T P, DEUTER I, DATTA J. Cast polyurethanes obtained from reactive recovered polyol intermediates via crude glycerine decomposition process[J]. Reactive and Functional Polymers, 2017, 119: 20-25.
42	SHEN L, YIN H, WANG A, et al. Liquid phase dehydration of glycerol to acrolein catalyzed by silicotungstic, phosphotungstic, and phosphomolybdic acids[J]. Chemical Engineering Journal, 2012, 180: 277-283.
43	MA T, DING J, SHAO R, et al. Dehydration of glycerol to acrolein over Wells-Dawson and Keggin type phosphotungstic acids supported on MCM-41 catalysts[J]. Chemical Engineering Journal, 2017, 316: 797-806.
44	KONAKA A, TAGO T, YOSHIKAWA T, et al. Conversion of biodiesel-derived crude glycerol into useful chemicals over a zirconia-iron oxide catalyst[J]. Industrial & Engineering Chemistry Research, 2013, 52(44): 15509-15515.
45	LIU R, LYU S, WANG T. Sustainable production of acrolein from biodiesel-derived crude glycerol over H₃PW₁₂O₄₀ supported on Cs-modified SBA-15[J]. Journal of Industrial and Engineering Chemistry, 2016, 37: 354-360.
46	SERESHKI B R, BALAN S J, PATIENCE G S, et al. Reactive vaporization of crude glycerol in a fluidized bed reactor[J]. Industrial & Engineering Chemistry Research, 2010, 49(3): 1050-1056.
47	CHENG L, LIU L, YE X P. Acrolein production from crude glycerol in sub-and super-critical water[J]. Journal of the American Oil Chemists’ Society, 2013, 90(4): 601-610.
48	TALEBIAN-KIAKALAIEH A, AMIN N A S. Thermo-kinetic and diffusion studies of glycerol dehydration to acrolein using HSiW-γ-Al₂O₃ supported ZrO₂ solid acid catalyst[J]. Renewable Energy, 2017, 114: 794-804.
49	ZHANG E, ZHAI W, LUO Y, et al. Acclimatization of microbial consortia to alkaline conditions and enhanced electricity generation[J]. Bioresource Technology, 2016, 211: 736-742.
50	RAGO L, BAEZA J A, GUISASOLA A. Increased performance of hydrogen production in microbial electrolysis cells under alkaline conditions[J]. Bioelectrochemistry, 2016, 109: 57-62.
51	MONTPART N, RAGO L, BAEZA J A, et al. Hydrogen production in single chamber microbial electrolysis cells with different complex substrates[J]. Water Research, 2015, 68: 601-615.
52	ZHANG Z, XIN L, QI J, et al. Supported Pt, Pd and Au nanoparticle anode catalysts for anion-exchange membrane fuel cells with glycerol and crude glycerol fuels[J]. Applied Catalysis B: Environmental, 2013, 136/137: 29-39.
53	MAYA-CORNEJO J, GUERRA-BALCáZAR M, ARJONA N, et al. Electrooxidation of crude glycerol as waste from biodiesel in a nanofluidic fuel cell using Cu@Pd/C and Cu@Pt/C[J]. Fuel, 2016, 183: 195-205.
54	BADIA-FABREGAT M, RAGO L, BAEZA J A, et al. Hydrogen production from crude glycerol in an alkaline microbial electrolysis cell[J]. International Journal of Hydrogen Energy, 2019, 44(32): 17204-17213.

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