生物质化学工程 ›› 2024, Vol. 58 ›› Issue (2): 64-72.doi: 10.3969/j.issn.1673-5854.2024.02.008
• 综述评论 • 上一篇
收稿日期:
2023-05-26
出版日期:
2024-03-30
发布日期:
2024-03-22
通讯作者:
李化毅
E-mail:lihuayi@iccas.ac.cn
作者简介:
李化毅, 副研究员, 硕士生导师, 研究领域: 聚烯烃催化剂和聚烯烃新材料; E-mail: lihuayi@iccas.ac.cnJian CHENG1,2, Shiwen LI1,3, Zhanfang MA2, Huayi LI1,*()
Received:
2023-05-26
Online:
2024-03-30
Published:
2024-03-22
Contact:
Huayi LI
E-mail:lihuayi@iccas.ac.cn
摘要:
油酸甲酯与乙烯复分解反应是一类特殊的烯烃复分解反应,经过交叉复分解反应获得1-癸烯和9-癸烯酸甲酯两种端烯中间体,同时存在竞争性反应生成9-十八烯和9-十八烯-1,18-二甲酯。催化剂的选择对该反应的速率和选择性起着决定作用,随着高效、稳定的商业化钌基催化剂问世,逐渐拓展了该反应的工业化应用范围,但对该反应的研究目前仍然存在工艺条件不够完善、产物分布宽、均相催化剂昂贵且回收困难、非均相催化剂负载活性差等问题。本文详细阐述了油酸甲酯与乙烯复分解反应的机理,以催化剂的发展为轴线,从工艺条件、催化剂种类、产物工业应用等方面介绍了该反应的研究历程;以油酸甲酯转化率、产物产率和选择性、催化剂周转数(TON)值为基准,系统评估了该反应的研究进展。同时建议在今后探索中,除了对催化剂进行开发以外,还应结合实际条件对整个反应体系进行优化,实现反应、检测和分离一体化。
中图分类号:
程键, 李世文, 马占芳, 李化毅. 油酸甲酯与乙烯复分解反应的研究进展[J]. 生物质化学工程, 2024, 58(2): 64-72.
Jian CHENG, Shiwen LI, Zhanfang MA, Huayi LI. Research Progress in Double Decomposition Reaction of Methyl Oleate and Ethylene[J]. Biomass Chemical Engineering, 2024, 58(2): 64-72.
表1
早期用于乙烯复分解反应的过渡金属催化剂"
催化剂种类type of catalyst | 温度/K temperature | 乙烯压力/MPa ethylene pressure | 反应时间/h reaction time | 转化率/% conversion rate | 选择性/% selectivity | 产率/% productivity | TON值TON value | 文献ref. |
WCl6-Me4Sn | 343 | 0.2 | 20 | 68 | — | — | — | [ |
Re2O7-Al2O3-Me4Sn | 293 | 0.2 | 20 | 75 | — | — | — | [ |
Mo(NAd)(CHCMe2Ph) | — | 0.4 | 15 | 95 | 99 | 95 | 4 750 | [ |
WO(Ns)2SiO2 | 373 | 0.5 | 1 | 65 | 90 | — | 65 | [ |
MTO/ZnAl2O4 | 318 | 1 | 5 | 52 | — | 58 | 4.7 | [ |
表2
部分钌基金属催化剂"
催化剂种类type of catalyst | 温度/K temperature | 乙烯压力/MPa ethylene pressure | 反应时间/h reaction time | 转化率/% conversion rate | 选择性/% selectivity | 产率/% productivity | TON值TON value | 文献ref. |
Grubbs Ⅰ | 303 | 0.4 | 3 | 80 | 100 | — | 2 980 | [ |
Grubbs Ⅱ | 313 | 0.2 | 2 | 94.9 | 100 | 94.9 | — | [ |
Ru6 | 333 | 1 | 4 | 57 | 35 | 61 | 1 750 | [ |
Ru7 | 303 | 1 | 0.5 | 42 | 83 | 35 | 26 000 | [ |
Ru9 | 323 | 1 | 3 | 52 | 97 | 74 | 100 000 | [ |
Ru10 | 323 | 1 | 3 | 73 | 97 | 74 | 3 125 | [ |
1 |
LOZANO F J , LOZANO R , FREIER P , et al. New perspectives for green and sustainable chemistry and engineering: Approaches from sustainable resource and energy use, management, and transformation[J]. Journal of Cleaner Production, 2018, 172, 227- 232.
doi: 10.1016/j.jclepro.2017.10.145 |
2 |
BIERMANN U , BIERMANN U , MEIER M , et al. Oils and fats as renewable raw materials in chemistry[J]. Angewandte Chemie International Edition, 2011, 50 (17): 3854- 3871.
doi: 10.1002/anie.201002767 |
3 | STYMNE S . Replacing fossil oil with plant oils-for what?[J]. Biophysical Journal, 2012, 102 (3): 41- 42. |
4 |
BAUMANN H , BÜHLER M , FOCHEM H , et al. Natural fats and oils: Renewable raw materials for the chemical industry[J]. Angewandte Chemie International Edition, 1988, 27 (1): 41- 62.
doi: 10.1002/anie.198800411 |
5 | HILL K . Fats and oils as oleochemical raw materials[J]. Pure & Applied Chemistry, 2000, 72 (7): 1255- 1264. |
6 |
SRIKANTH V , PRASAD R B N , POORNACHANDRA Y , et al. Synthesis of dihydrosterculic acid-based monoglucosyl diacylglycerol and its analogues and their biological evaluation[J]. European Journal of Medicinal Chemistry, 2016, 109, 134- 145.
doi: 10.1016/j.ejmech.2015.12.048 |
7 | 王林祥, 常敏. 全球乙烯供需分析及预测[J]. 世界石油工业, 2021, 28 (5): 8- 15. |
8 |
BRADSHAW C , HOWMAN E J , TURNER L . Olefin dismutation: Reactions of olefins on cobalt oxide-molybdenum oxide-alumina[J]. Journal of Catalysis, 1967, 7 (3): 269- 276.
doi: 10.1016/0021-9517(67)90105-4 |
9 | 张耀, 段庆华, 刘依农, 等. 离子液体催化1-癸烯齐聚制备聚α-烯烃的研究[J]. 石油炼制与化工, 2011, 42 (11): 62- 65. |
10 | 贺丽丽, 丁洪生, 刘进, 等. 新型离子液体催化1-癸烯齐聚反应研究[J]. 化工科技, 2010, 18, 7- 10. |
11 |
BEHR A , KREMA S , KAMPER A . Ethenolysis of ricinoleic acid methyl ester: An efficient way to the oleochemical key substance methyl dec-9-enoate[J]. RSC Advances, 2012, 2 (33): 12775- 12781.
doi: 10.1039/c2ra22499b |
12 | BROU G , REES A H . A synthesis of pure methyl 9-oxodecanoate, an intermediate in the synthesis of queen honeybee ester[J]. Journal of Apicultural Research, 2015, 22 (1): 22- 26. |
13 | 谢丹华, 高尚灿, 陈峰. 以油酸为起始原料的顺式-9-十八烯的合成[J]. 楚雄师范学院学报, 2015, 30 (9): 3- 5. |
14 | 戴晴, 刘冰倩, 李祥, 等. 烷胺型酸性离子液体的制备及其催化合成油酸甲酯的研究[J]. 能源化工, 2022, 43 (5): 37- 42. |
15 | CHATTERJEE A , ELIASSON S H H , JENSEN V R . Selective production of linear alpha-olefins via catalytic deoxygenation of fatty acids and derivatives[J]. Catalysis Science & Technology, 2018, 8 (6): 1487- 1499. |
16 | NICKEL A, PEDERSON R L. Commercial potential of olefin metathesis of renewable feedstocks[M]//GRELA K. Olefin Metathesis: Theory and Practice. Hoboken: John Wiley & Sons, Inc., 2014: 335-348. |
17 | GRUBBS R H . Olefin-metathesis catalysts for the preparation of molecules and materials(Nobel Lecture 2005)[J]. Advanced Synthesis & Catalysis, 2007, 349 (1/2): 34- 40. |
18 | 舒恒毅, 郑志锋, 刘守庆, 等. 油酸甲酯烯烃复分解制备长链终端烯烃化学品探究[J]. 林业工程学报, 2021, 6 (4): 7- 19. |
19 | CHAUVIN Y . Olefin metathesis: The early days(Nobel Lecture 2005)[J]. Advanced Synthesis & Catalysis, 2007, 349 (1/2): 27- 33. |
20 | 张慧青. 钌烯烃复分解催化剂的合成以及活性测试[D]. 天津: 天津大学, 2020. |
21 | 王溯, 张友璐, 巴妍妍, 等. 立体选择性烯烃复分解反应的研究及应用[J]. 有机化学, 2020, 40 (9): 2725- 2741. |
22 | 舒恒毅, 郑志锋, 刘守庆, 等. 烯烃复分解反应在植物油脂制备烯烃衍生品中的应用[J]. 广东化工, 2020, 47 (22): 5- 23. |
23 | 时萌珣, 刘前, 刘建, 等. 双环戊二烯开环易位聚合反应用催化剂的研究进展[J]. 上海塑料, 2021, 49 (1): 12- 20. |
24 | 温鹏, 梁宇翔, 贺景坚, 等. 乙烯复分解反应在生物质合成烯烃化学品中的研究进展[J]. 化工进展, 2021, 40 (增刊2): 64- 74. |
25 | 邓亚奎. 机械力诱导发光和自修复高分子材料的合成与性质研究[D]. 天津: 天津大学, 2020. |
26 | 刘娟. 丁腈橡胶催化加氢及其功能化改性研究[D]. 太原: 中北大学, 2023. |
27 |
LOVE J A , MORGAN J P , TENKA T M , et al. A practical and highly active ruthenium-based catalyst that effects the cross metathesis of acrylonitrile[J]. Angewandte Chemie International Edition, 2002, 41 (21): 4035- 4037.
doi: 10.1002/1521-3773(20021104)41:21<4035::AID-ANIE4035>3.0.CO;2-I |
28 | BUJOK R , BIENIEK M , MASNYK M , et al. Ortho- and para-substituted Hoveyda-Grubbs carbenes.An improved synthesis of highly efficient metathesis initiators[J]. Cheminform, 2005, 36 (6): 6894- 6896. |
29 | MA J F, HOU M M, TANG H D, et al. REM sleep behavior disorder was associated with Parkinson's disease: A community-based study[J/OL]. BMC Neurology, 2016, 16: 123[2023-05-10]. https://doi.org/10.1186/s12883-016-0640-1. |
30 | BOSMA R , AARDWEG F , MOL J C . Cometathesis of methyl oleate and ethylene; a direct route to methyl dec-9-enoate[J]. Cheminform, 1981, 13 (12): 1132- 1133. |
31 |
MARINESCU S C , SCHROCK R R , MÜLLER P , et al. Ethenolysis reactions catalyzed by imido alkylidene monoaryloxide monopyrrolide(MAP) complexes of molybdenum[J]. Journal of the American Chemical Society, 2009, 131 (31): 10840- 10841.
doi: 10.1021/ja904786y |
32 | SIBEIJIN M , MOl J C . Ethenolysis of methyl oleate over supported Re-based catalysts[J]. Journal of Molecular Catalysis, 1992, 76 (1/2/3): 345- 358. |
33 |
MANDELLI D , JANNINI M J D M , BUFFON R , et al. Ethenolysis of esters of vegetable oils: Effect of B2O3, addition to Re2O7/SiO2·Al2O3-SnBu4, and CH3ReO3/SiO2·Al2O3, metathesis catalysts[J]. Journal of the American Oil Chemists' Society, 1996, 73 (2): 229- 232.
doi: 10.1007/BF02523900 |
34 |
ROUGE P , SZETO K C , et al. Ethenolysis of renewable methyl oleate catalyzed by readily accessible supported group Ⅵ oxo catalysts[J]. Organometallics, 2020, 39 (7): 1105- 1111.
doi: 10.1021/acs.organomet.9b00823 |
35 | LEE M , HAN Y H , HWANG D W . Cross-metathesis of methyl oleate with ethylene over methyltrioxorhenium supported on ZnAl2O4 as a heterogeneous catalyst[J]. Catalysis Communications, 2020, 144, 229- 232. |
36 |
NIERES P D , ZELIN J , TRASARTI A F , et al. Valorisation of vegetable oils by heterogeneous catalysis via metathesis reactions[J]. Current Opinion in Green and Sustainable Chemistry, 2018, 10, 1- 5.
doi: 10.1016/j.cogsc.2018.02.001 |
37 |
BURDETT K A , HARRIS L D , MARGL P , et al. Renewable monomer feedstocks via olefin mtathesis fundamental mechanistic studies of methyl oleate ethenolysis with the first-generation Grubbs catalyst[J]. Organometallics, 2004, 23 (9): 2027- 2047.
doi: 10.1021/om0341799 |
38 | WANG M, CHEN M J, FANG Y M, et al. Highly efficient conversion of plant oil to bio-aviation fuel and valuable chemicals by combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating[J/OL]. Biotechnology for Biofuels, 2018, 11: 30[2023-05-10]. https://doi.org/10.1186/s13068-018-1020-4. |
39 | 龙烁. 热稳定性钌催化剂在油酸甲酯复分解及二烯烃橡胶降解上的应用[D]. 呼和浩特: 内蒙古大学, 2022. |
40 |
ZHANG J , SONG S , WANG X , et al. Ruthenium-catalyzed olefin metathesis accelerated by the steric effect of the backbone substituent in cyclic(alkyl)(amino) carbenes[J]. Chemical Communications, 2013, 49 (82): 9491- 9493.
doi: 10.1039/c3cc45823g |
41 |
MARX V M , SULLIVAN A H , MWLAIMI M , et al. Cyclic alkyl amino carbene(CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis[J]. Angewandte Chemie International Edition, 2015, 54 (6): 1919- 1923.
doi: 10.1002/anie.201410797 |
42 |
BYUN S , PARK S , CHOI Y , et al. Highly efficient ethenolysis and propenolysis of methyl oleate catalyzed by abnormal n-heterocyclic carbene ruthenium complexes in combination with a phosphine-copper cocatalyst[J]. ACS Catalysis, 2020, 10 (18): 10592- 10601.
doi: 10.1021/acscatal.0c02018 |
43 |
BYUN S , PARK D A , KIM S , et al. Highly selective ethenolysis with acyclic-aminooxycarbene ruthenium catalysts[J]. Inorganic Chemistry Frontiers, 2022, 9 (2): 323- 331.
doi: 10.1039/D1QI01132D |
44 |
WYREBEK P , MALECKI P , SYTNICZUK A , et al. Looking for the Noncyclic(amino)(alkyl)carbene ruthenium catalyst for ethenolysis of ethyl oleate: Selectivity is on target[J]. ACS Omega, 2018, 3 (12): 18481- 18488.
doi: 10.1021/acsomega.8b03119 |
45 |
MAYNARD H D , GRUBBS R H . Purification technique for the removal of ruthenium from olefin metathesis reaction products[J]. Tetrahedron Letters, 1999, 40 (22): 4137- 4140.
doi: 10.1016/S0040-4039(99)00726-1 |
46 |
PAQUTTE L A , SCHLO J D , EFREMOV I , et al. A convenient method for removing all highly-colored byproducts generated during olefin metathesis reactions[J]. Organic Letters, 2000, 2 (9): 1259- 1261.
doi: 10.1021/ol000036w |
47 |
YU M A , YANG K L , GEROG G I . A convenient method for the efficient removal of ruthenium byproducts generated during olefin metathesis reactions[J]. Organic Letters, 2001, 3 (9): 1411- 1413.
doi: 10.1021/ol010045k |
48 |
CHO J H , KIM B M . An efficient method for removal of ruthenium byproducts from olefin metathesis reactions[J]. Organic Letters, 2003, 5 (4): 531- 533.
doi: 10.1021/ol027423l |
49 | VOS D , DAMS M , SELS B F , et al. Ordered mesoporous and microporous molecular sieves functionalized with transition metal complexes as catalysts for selective organic transformations[J]. ChemInform, 2002, 34 (10): 3615- 3640. |
50 |
BALCAR H , SHINDE T , ZILKOVA N , BASTL Z . Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves MCM-41 and SBA-15[J]. Beilstein Journal of Organic Chemistry, 2011, 7, 22- 28.
doi: 10.3762/bjoc.7.4 |
51 |
WANG M S , XU G , ZHANG Z J , et al. Inorganic-organic hybrid photochromic materials[J]. Chemical Communications, 2010, 46 (3): 361- 376.
doi: 10.1039/B917890B |
52 |
YANG H Q , MA Z C , ZHOU T , et al. Encapsulation of an olefin metathesis catalyst in the nanocages of SBA-1:Facile preparation, high encapsulation efficiency, and high activity[J]. ChemCatChem, 2013, 5 (8): 2278- 2287.
doi: 10.1002/cctc.201300021 |
53 |
CHOŁUJ A , ZIELIŃSKI A , GRELA K , et al. Metathesis@MOF: Simple and robust immobilization of olefin metathesis catalysts inside(Al)MIL-101-NH2[J]. ACS Catalysis, 2016, 6 (10): 6343- 6349.
doi: 10.1021/acscatal.6b01048 |
54 |
KORZYNSKI M D , CONSOLI D F , ZHANG S . Activation of methyltrioxorhenium for olefin metathesis in a zirconium-based mtal-organic framework[J]. Journal of the American Chemical Society, 2018, 140 (22): 6956- 6960.
doi: 10.1021/jacs.8b02837 |
55 |
CHOŁUJ A , KARCZYKOWSKI R , CHMIELEWSKI M J . Simple and robust immobilization of a ruthenium olefin metathesis catalyst inside MOFs by acid-base reaction[J]. Organometallics, 2019, 38 (18): 3392- 3396.
doi: 10.1021/acs.organomet.9b00281 |
56 | MOHAN B, KUMAR S, XI H, et al. Fabricated metal-organic frameworks(MOFs) as iuminescent and electrochemical biosensors for cancer biomarkers detection[J/OL]. Biosens Bioelectron, 2022, 197: 113738[2023-05-10]. https://doi.org/10.1016/j.bios.2021.113738. |
57 | NIERES P D, VAILLARD V A, ZELÍN J, et al. Stability of a silica-supported second generation Hoveyda-Grubbs catalyst under atmospheric conditions: Experimental and Computational Studies[J/OL]. ChemCatChem, 2023, 15(10): e 202300010[2023-05-10]. https://doi.org/10.1002/cctc.202300010. |
58 | BERLO B , HOUTHOOFD K , SELS B F , et al. Silica immobilized second generation Hoveyda-Grubbs: A convenient, recyclable and storageable heterogeneous solid catalyst[J]. Advanced Synthesis & Catalysis, 2008, 350 (13): 1949- 1953. |
59 |
SHINDE T , ZILKOVA N , HANKOVA V , et al. Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves: The influence of pore size on the catalyst activity[J]. Catalysis Today, 2012, 179 (1): 123- 129.
doi: 10.1016/j.cattod.2011.06.012 |
60 | BERLO B V , HOUTHOOFD K , SELS B F , et al. Cheminform abstract: Silica-immobilized second generation Hoveyda—Grubbs: A convenient, recyclable and storageable heterogeneous solid catalyst[J]. ChemInform, 2009, 40 (2): 2- 48. |
61 | NIERES P D , ZELIN J , TRASARTI A F , et al. Heterogeneous catalysis for valorisation of vegetable oils via metathesis reactions: Ethenolysis of methyl oleate[J]. Catalysis Science & Technology, 2016, 6 (17): 6561- 6568. |
62 | ZHU Y , LOO K , NG H , et al. Magnetic nanoparticle supported second generation Hoveyda-Grubbs catalyst for metathesis of unsaturated fatty acid esters[J]. Advanced Synthesis & Catalysis, 2009, 351 (16): 2650- 2656. |
63 |
PARK C V , WINGERDEN M M , HAN S Y , et al. Low pressure ethenolysis of renewable methyl oleate in a microchemical system[J]. Organic Letters, 2011, 13 (9): 2398- 2401.
doi: 10.1021/ol200634y |
64 | FUKUYAMAT , SATO M , RYU I . Adventures in inner space: Microflow systems for practical organic synthesis[J]. Cheminform, 2008, 2008 (2): 151- 163. |
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