微波强化酯交换反应制备生物柴油研究进展

doi:10.16085/j.issn.1000-6613.2021-2657

摘要/Abstract

摘要：

在碳达峰、碳中和的目标背景下，生物柴油被认为是替代化石燃料最有前途的新型能源之一。作为新型的加热方式，微波强化技术克服了传统加热方式下受热不均等缺点，在与不同催化体系偶联的过程中显著促进了酯交换反应的效率，较大幅度地提高了生物柴油的产率。本文归纳了微波技术强化酯交换反应制备生物柴油的优势，介绍了微波强化技术偶联均相催化、非均相催化、离子液体催化以及酶催化技术在生物柴油制备领域的研究进展，阐述了微波强化技术偶联各催化体系的利弊。从催化效率和环保等方面考虑，微波强化偶联非均相催化和酶催化具有更优的研究前景。最后，就该领域的研究方向提出几点展望与建议。

关键词: 微波强化技术, 酯交换反应, 生物柴油

Abstract:

In the context of carbon peaking and carbon neutrality, biodiesel is considered to be one of the most promising alternatives to fossil fuels. As a novel heating method, microwave-intensified technology can overcome some disadvantages, such as uneven heating etc., compared with traditional heating. Therefore, it can promote transesterification efficiency significantly and improve biodiesel yield greatly, coupled with different catalytic systems. This review first summarizes the advantages of microwave-assisted intensification of transesterification to prepare biodiesel. Then, the research status of microwave-intensified technology coupled with homogeneous catalysis, heterogeneous catalysis, ionic liquid catalysis as well as enzyme catalysis is especially introduced, and the corresponding pros and cons of each catalytic systems under microwave-intensified technology is analyzed. In terms of the catalytic efficiency and environmental-friend, it is illustrated that microwave-intensified technology coupled with heterogeneous catalysis and enzymatic catalysis is widely used in biodiesel preparation. Finally, some prospects and suggestions are proposed for the research field.

Key words: microwave-intensified technology, transesterification, biodiesel

中图分类号:

X592

朱长辉, 朱文超, 罗嘉, 田保河, 孙佳琳, 邹志云. 微波强化酯交换反应制备生物柴油研究进展[J]. 化工进展, 2022, 41(10): 5145-5154.

ZHU Changhui, ZHU Wenchao, LUO Jia, TIAN Baohe, SUN Jialin, ZOU Zhiyun. Recent advances in microwave-intensified transesterification for biodiesel preparation[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5145-5154.

图/表 14

参考文献 53

1	王笃政, 孙永杰, 孙彬峰, 等. 微波强化化工过程技术进展[J]. 精细与专用化学品, 2012, 20(12): 38-41.
	WANG D Z, SUN Y J, SUN B F, et al. Review on the intensification of chemical engineering processes by microwave[J]. Fine and Specialty Chemicals, 2012, 20(12): 38-41.
2	张伟, 韩立峰. 国内外生物柴油研究现状及发展趋势[J]. 化工管理, 2021(12): 72-73.
	ZHANG W, HAN L F. Research status and development trend of biodiesel at home and abroad[J]. Chemical Enterprise Management, 2021(12): 72-73.
3	张梦妮, 程敢, 李玉龙. 生物柴油的制备及其在浮选中的应用进展[J]. 洁净煤技术, 2021, 27(1): 34-40.
	ZHANG M N, CHENG G, LI Y L. Research progress on the preparation of biodiesel and its application in flotation[J]. Clean Coal Technology, 2021, 27(1): 34-40.
4	李顶杰, 吕勃. 推动废弃油脂制生物燃料产业发展[N]. 中国石油报, 2021-09-28(6).
5	APPLETON T J, COLDER R I, KINGMAN S W, et al. Microwave technology for energy-efficient processing of waste[J]. Applied Energy, 2005, 81(1): 85-113.
6	ZHANG F H, ZHOU T Y, LIU Y J, et al. Microwave synthesis and actuation of shape memory polycaprolactone foams with high speed[J]. Scientific Reports, 2015, 5: 11152.
7	潘凯, 吴炼, 钟浪声, 等. 酯交换制备生物柴油过程强化技术研究进展[J]. 大众科技, 2017, 19(5): 39-43.
	PAN K, WU L, ZHONG L S, et al. Progress in biodiesel production via process intensification[J]. Popular Science & Technology, 2017, 19(5): 39-43.
8	MOTASEMI F, ANI F N. A review on microwave-assisted production of biodiesel[J]. Renewable and Sustainable Energy Reviews, 2012, 16(7): 4719-4733.
9	蒋波, 张晓东, 孙立, 等. 微波促进生物柴油制备的研究进展[J]. 化工进展, 2010, 29(11): 2057-2065.
	JIANG B, ZHANG X D, SUN L, et al. Advances in microwave promoted biodiesel synthesis[J]. Chemical Industry and Engineering Progress, 2010, 29(11): 2057-2065.
10	KALSUM U, MAHMUDDIN, MAHFUD M, et al. Biodiesel production from Chlorella vulgaris via homogenous acid catalyzed in situ transesterification with microwave irradiation[J]. IOP Conference Series: Earth and Environmental Science, 2018, 175: 012018.
11	ZHANG S, ZU Y G, FU Y J, et al. Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst[J]. Bioresource Technology, 2010, 101(3): 931-936.
12	YUAN H, SHU Q. Synthesis of biodiesel from castor oil catalyzed by cesium phosphotungstate with the assistance of microwave[J]. Applied Mechanics and Materials, 2013, 291/292/293/294: 300-306.
13	NAYAK M G, VYAS A P. Optimization of microwave-assisted biodiesel production from Papaya oil using response surface methodology[J]. Renewable Energy, 2019, 138: 18-28.
14	LERTSATHAPORNSUK V, PAIRINTRA R, KRISNANGKURA K. Direct conversion of used vegetable oil to biodiesel and its use as an alternative fuel for compression ignition engine[C]// Proc First Int Conf Sustainable Energy and Green Architecture. 2003: SE091-SE096.
15	HERNANDO J, LETON P, MATIA M P, et al. Biodiesel and FAME synthesis assisted by microwaves: homogeneous batch and flow processes[J]. Fuel, 2007, 86(10/11): 1641-1644.
16	SAIFUDDIN N M, CHUA K H. Production of ethyl ester (biodiesel) from used frying oil: optimization of transesterification process using microwave irradiation[J]. Malaysian Journal of Chemistry, 2004, 6(1): 77-82.
17	SILITONGA A S, SHAMSUDDIN A H, MAHLIA T M I, et al. Biodiesel synthesis from Ceiba pentandra oil by microwave irradiation-assisted transesterification: ELM modeling and optimization[J]. Renewable Energy, 2020, 146: 1278-1291.
18	ENCINAR J M, GONZÁLEZ J F, MARTÍNEZ G, et al. Soybean oil transesterification by the use of a microwave flow system[J]. Fuel, 2012, 95: 386-393.
19	KUMAR R, KUMAR G R, CHANDRASHEKAR N. Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production[J]. Bioresource Technology, 2011, 102(11): 6617-6620.
20	LIN Y C, HSU K H, LIN J F. Rapid palm-biodiesel production assisted by a microwave system and sodium methoxide catalyst[J]. Fuel, 2014, 115: 306-311.
21	CHEN K S, LIN Y C, HSU K H, et al. Improving biodiesel yields from waste cooking oil by using sodium methoxide and a microwave heating system[J]. Energy, 2012, 38(1): 151-156.
22	CHELLAPPAN S, APARNA K, CHINGAKHAM C, et al. Microwave assisted biodiesel production using a novel Brønsted acid catalyst based on nanomagnetic biocomposite[J]. Fuel, 2019, 246: 268-276.
23	GULDHE A, SINGH B, RAWAT I, et al. Synthesis of biodiesel from Scenedesmus sp. by microwave and ultrasound assisted in situ transesterification using tungstated zirconia as a solid acid catalyst[J]. Chemical Engineering Research and Design, 2014, 92(8): 1503-1511.
24	FATIMAH I, RUBIYANTO D, TAUSHIYAH A, et al. Use of ZrO₂ supported on bamboo leaf ash as a heterogeneous catalyst in microwave-assisted biodiesel conversion[J]. Sustainable Chemistry and Pharmacy, 2019, 12: 100129.
25	YUAN H, MA X Q, HE J, et al. Surface characterization of sulfated iron oxide and its synthesis of biodiesel under microwave radiation[J]. International Journal of Chemical Reactor Engineering, 2018, 16(2): 20160161.
26	MAZZOCCHIA C, MODICA G, KADDOURI A, et al. Fatty acid methyl esters synthesis from triglycerides over heterogeneous catalysts in the presence of microwaves[J]. Comptes Rendus Chimie, 2004, 7(6/7): 601-605.
27	HSIAO M C, LIN C C, CHANG Y H. Microwave irradiation-assisted transesterification of soybean oil to biodiesel catalyzed by nanopowder calcium oxide[J]. Fuel, 2011, 90(5): 1963-1967.
28	LAWAN I, GARBA Z N, ZHOU W M, et al. Synergies between the microwave reactor and CaO/zeolite catalyst in waste lard biodiesel production[J]. Renewable Energy, 2020, 145: 2550-2560.
29	QU S K, CHEN C, GUO M L, et al. Microwave-assisted in situ transesterification of Spirulina platensis to biodiesel using PEG/MgO/ZSM-5 magnetic catalyst[J]. Journal of Cleaner Production, 2021, 311: 127490.
30	TANGY A, PULIDINDI I N, GEDANKEN A. SiO₂ beads decorated with SrO nanoparticles for biodiesel production from waste cooking oil using microwave irradiation[J]. Energy & Fuels, 2016, 30(4): 3151-3160.
31	NAOR E O, KOBERG M, GEDANKEN A. Nonaqueous synthesis of SrO nanopowder and SrO/SiO₂ composite and their application for biodiesel production via microwave irradiation[J]. Renewable Energy, 2017, 101: 493-499.
32	YE B, QIU F X, SUN C J, et al. Transesterification of soybean oil to biodiesel in a microwave-assisted heterogeneous catalytic system[J]. Chemical Engineering & Technology, 2014, 37(2): 283-292.
33	WANG Y Y, LEE D J, CHEN B H. Low-Al zeolite beta as a heterogeneous catalyst in biodiesel production from microwave-assisted transesterification of triglycerides[J]. Energy Procedia, 2014, 61: 918-921.
34	NAYEBZADEH H, SAGHATOLESLAMI N, HAGHIGHI M, et al. Influence of fuel type on microwave-enhanced fabrication of KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst for biodiesel production via microwave heating[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 75: 148-155.
35	IKENAGA K, HAMADA A, INOUE T, et al. Biodiesel production using metal oxide catalysts under microwave heating[J]. International Journal of Biomass and Renewables, 2017, 6(2): 23-26.
36	HANDAYANI P A, ABDULLAH A, HADIYANTO H. Biodiesel production from Nyamplung (Calophyllum inophyllum) oil using ionic liquid as a catalyst and microwave heating system[J]. Bulletin of Chemical Reaction Engineering & Catalysis, 2017, 12(2): 293.
37	敖红伟, 王淑波. 微波协同功能化酸性离子液体催化制备生物柴油工艺研究[J]. 粮食与油脂, 2017, 30(10): 50-53.
	AO H W, WANG S B. Study on the preparation of biodiesel by microwave assisted functionalized acidic ionic liquid[J]. Cereals & Oils, 2017, 30(10): 50-53.
38	DING H, YE W, WANG Y Q, et al. Process intensification of transesterification for biodiesel production from palm oil: microwave irradiation on transesterification reaction catalyzed by acidic imidazolium ionic liquids[J]. Energy, 2018, 144: 957-967.
39	苗长林, 吕鹏梅, 王忠铭, 等. 微波辅助组合离子液体直接制备微藻生物柴油[J]. 太阳能学报, 2021, 42(2): 233-238.
	MIAO C L, LYU P M, WANG Z M, et al. Preparation of microalgae biodiesel by direct transesterification under microwave-assisted ionic liquid composite conditions[J]. Acta Energiae Solaris Sinica, 2021, 42(2): 233-238.
40	LIN Y C, YANG P M, CHEN S C, et al. Improving biodiesel yields from waste cooking oil using ionic liquids as catalysts with a microwave heating system[J]. Fuel Processing Technology, 2013, 115: 57-62.
41	MAJEWSKI M W, POLLACK S A, CURTIS-PALMER V A. Diphenylammonium salt catalysts for microwave assisted triglyceride transesterification of corn and soybean oil for biodiesel production[J]. Tetrahedron Letters, 2009, 50(37): 5175-5177.
42	NOGUEIRA B M, CARRETONI C, CRUZ R, et al. Microwave activation of enzymatic catalysts for biodiesel production[J]. Journal of Molecular Catalysis B: Enzymatic, 2010, 67(1/2): 117-121.
43	CARVALHO A K F, BENTO H B S, IZÁRIO FILHO H J, et al. Approaches to convert Mucor circinelloides lipid into biodiesel by enzymatic synthesis assisted by microwave irradiations[J]. Renewable Energy, 2018, 125: 747-754.
44	RÓS P C M DA, DE CASTRO H F, CARVALHO A K F, et al. Microwave-assisted enzymatic synthesis of beef tallow biodiesel[J]. Journal of Industrial Microbiology and Biotechnology, 2012, 39(4): 529-536.
45	RÓS P C M DA, FREITAS L, PEREZ V H, et al. Enzymatic synthesis of biodiesel from palm oil assisted by microwave irradiation[J]. Bioprocess and Biosystems Engineering, 2013, 36(4): 443-451.
46	ZHANG Y H, XIA X X, DUAN M H, et al. Green deep eutectic solvent assisted enzymatic preparation of biodiesel from yellow horn seed oil with microwave irradiation[J]. Journal of Molecular Catalysis B: Enzymatic, 2016, 123: 35-40.
47	PANADARE D C, RATHOD V K. Microwave assisted enzymatic synthesis of biodiesel with waste cooking oil and dimethyl carbonate[J]. Journal of Molecular Catalysis B: Enzymatic, 2016, 133: S518-S524.
48	YU D H, WANG C M, YIN Y N, et al. A synergistic effect of microwave irradiation and ionic liquids on enzyme-catalyzed biodiesel production[J]. Green Chemistry, 2011, 13(7): 1869.
49	PATIL P D, REDDY H, MUPPANENI T, et al. In situ ethyl ester production from wet algal biomass under microwave-mediated supercritical ethanol conditions[J]. Bioresource Technology, 2013, 139: 308-315.
50	GOLE V L, GOGATE P R. Intensification of synthesis of biodiesel from non-edible oil using sequential combination of microwave and ultrasound[J]. Fuel Processing Technology, 2013, 106: 62-69.
51	KHEDRI B, MOSTAFAEI M, SAFIEDDIN ARDEBILI S M. A review on microwave-assisted biodiesel production[J]. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2019, 41(19): 2377-2395.
52	陈榆中. 微波反应器及其制备生物柴油的应用研究[D]. 无锡: 江南大学, 2014.
	CHEN Y Z. Study on microwave reactor and its application in the preparation of biodiesel[D]. Wuxi: Jiangnan University, 2014.
53	MOHAMAD AZIZ N A, YUNUS R, KANIA D, et al. Prospects and challenges of microwave-combined technology for biodiesel and biolubricant production through a transesterification: a review[J]. Molecules, 2021, 26(4): 788.

序号	催化剂	底物	微波功率/W	温度/℃	时间/min	醇/底物剂量比	生物柴油产率/%	参考文献
1	H₂SO₄	小球藻油脂	450	—	70	—	31.6	［10］
2	Cs_2.5H_0.5PW₁₂	文冠果油	—	60	10	12∶1	96.2	［11］
3	Cs_2.5H_0.5PW₁₂	蓖麻油	300	70	240	30∶1	90	［12］

序号	催化剂	底物	微波功率/W	温度/℃	时间/min	醇/底物剂量比	生物柴油产率/%	参考文献
1	H₂SO₄	小球藻油脂	450	—	70	—	31.6	［10］
2	Cs_2.5H_0.5PW₁₂	文冠果油	—	60	10	12∶1	96.2	［11］
3	Cs_2.5H_0.5PW₁₂	蓖麻油	300	70	240	30∶1	90	［12］

序号	催化剂	底物	微波功率/W	温度/℃	时间/min	醇/底物剂量比	生物柴油产率/%	参考文献
1	NaOH	木瓜籽油	700	62.2	3.3	9.5∶1	99	［13］
2	NaOH	WCO	1100	—	0.17	9∶1	100	［14］
3	NaOH	菜籽油	300	60	1	—	97	［15］
4	NaOH	WCO	750	60	10	6∶1	—	［16］
5	KOH	粗木棉油	850	—	6.47	3∶5	95.4	［17］
6	KOH	大豆油	70	65	15	12∶1	95.4	［18］
7	NaOH、KOH	水黄皮籽油	1200	60	5	6∶1	96	［19］
8	CH₃ONa	棕榈油	750	60～65	3	6∶1	99.5	［20］
9	CH₃ONa、NaOH	WCO	750	—	3	6∶1	97.9	［21］

序号	催化剂	底物	微波功率/W	温度/℃	时间/min	醇/底物剂量比	生物柴油产率/%	参考文献
1	NaOH	木瓜籽油	700	62.2	3.3	9.5∶1	99	［13］
2	NaOH	WCO	1100	—	0.17	9∶1	100	［14］
3	NaOH	菜籽油	300	60	1	—	97	［15］
4	NaOH	WCO	750	60	10	6∶1	—	［16］
5	KOH	粗木棉油	850	—	6.47	3∶5	95.4	［17］
6	KOH	大豆油	70	65	15	12∶1	95.4	［18］
7	NaOH、KOH	水黄皮籽油	1200	60	5	6∶1	96	［19］
8	CH₃ONa	棕榈油	750	60～65	3	6∶1	99.5	［20］
9	CH₃ONa、NaOH	WCO	750	—	3	6∶1	97.9	［21］

序号	催化剂	底物	微波功率/W	温度/℃	时间/min	醇/底物比	生物柴油产率/%	参考文献
1	nM-CP-SO₃H	鸡血藤油	—	65	45	11∶1	98.7	［22］
2	WO₃/ZrO₂	栅藻	651	120	20	45∶1	51.9	［23］
3	ZrO₂/BLA	大豆油	—	—	30	15∶1	92.8	［24］
4	SO₄^2-/Fe₂O₃	蓖麻油	300	65	180	30∶1	65.3	［25］
5	蒙脱石KSF	菜籽油	1000	170	60	9∶1	51	［26］