Synthesis of nitriles and pyridine bases from bio-based small molecules by catalytic amination

doi:10.16085/j.issn.1000-6613.2019-1722

Abstract

Abstract:

Synthesis of nitriles and pyridine base from bio-based small molecules by catalytic amination can not only reduce the dependency on fossil resources in the production of these kinds of chemicals, but also promote the sustainable development of bio-based small molecule industry. Herein, the latest development in the conversion of ethanol and glycerol to nitriles and pyridine bases via catalytic amination were reviewed including the research results of our group. Among which, acetonitrile can be produced from ethanol with high yield. Ethanol can also be converted to pyridine bases over a catalyst with dehydrogenation activity and suitable acidity. Glycerol can be converted to nitriles or pyridine bases via either one step or two-step process, in which perfect acidity, stronger dehydrogenation-hydrogenation activity and bigger surface areas of catalysts are key facts to enable the catalysts with good performances. Two-step process generally produced nitriles or pyridine bases with much higher yield than one-step process. Deactivation of the catalysts took place due to the coke formation by irreversible adsorption of imine intermediates on the acid sites. Most deactivated catalysts can be regenerated via calcination at high temperature and in the presence of oxygen.

Key words: catalytic amination, bio-based small molecules, ethanol, glycerin, nitriles, pyridine bases

摘要：

基于催化氨化反应以生物质基小分子合成腈类、吡啶碱等含氮化学品，不但可减少生产此类产品对化石资源的依赖，还可促进生物质基小分子产业的可持续发展。本文结合本文作者课题组的研究成果总结了近年来在乙醇、甘油催化氨化合成腈类、吡啶碱的最新研究进展。其中，乙醇可高收率地生产乙腈，也可在脱氢、适宜酸性催化剂催化下生成吡啶碱。甘油在适宜催化剂上既可以通过一步法也可以通过两步法转化为腈类和吡啶碱，其中催化剂适宜的酸性、较强的加氢-脱氢性能以及较大的比表面是决定生成何种目标产物的关键。采用两步法比一步法由甘油合成腈类和吡啶碱的收率明显提高。发现催化剂在使用中逐渐失活，而催化剂失活主要是由于亚胺中间体在催化剂酸中心的不可逆吸附，从而生成积炭所致。失活催化剂经高温有氧煅烧去除积炭可恢复其大部分活性。

关键词: 催化氨化, 生物质基小分子, 乙醇, 甘油, 腈类, 吡啶碱

CLC Number:

TQ426.94

He ZHU, Yuecheng ZHANG, Jiquan ZHAO. Synthesis of nitriles and pyridine bases from bio-based small molecules by catalytic amination[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3077-3085.

朱赫, 张月成, 赵继全. 基于催化氨化反应由生物质基小分子合成腈类和吡啶碱[J]. 化工进展, 2020, 39(8): 3077-3085.

References

1	ASLI Y, HIROMICHI K, MITSURU S, et al. Hydrothermal electrolysis of glycerol using a continuous flow reactor[J]. Industrial & Engineering Chemistry Research, 2010, 49(4): 1520-1525.
2	ZHENG Y G, CHEN X L, SHEN Y C. Commodity chemicals derived from glycerol, an important biorefinery feedstock[J]. Chemical Reviews, 2008, 108: 5227-5252.
3	陈小燕, 许敬亮, 袁振宏, 等. 马克斯克鲁维酵母制备生物质乙醇研究进展[J]. 新能源进展, 2014, 2(5): 364-371.
3	CHEN Xiaoyan, XU Jingliang, YUAN Zhenhong, et al. Studies in biomass ethanol production by kluyveromyces marxianus[J]. Advances in New and Renewable Energy, 2014, 2(5): 364-371.
4	姚倩. 生物质热化学催化氨化制备含氮化学品的研究[D]. 合肥: 中国科学技术大学, 2018.
4	YAO Qian. Studies on producing nitrogen-containing chemicals via thermo-catalytic conversion and ammonization of biomass[D]. Hefei: University of Science and Technology of China, 2018.
5	陈阳, 白鹏, 郭翔海. 绿色化学原则下国内外乙腈生产工艺分析[J]. 化工进展, 2019, 38(10): 4374-4388.
5	CHEN Yang, BAI Peng, GUO Xianghai. Analysis of the acetonitrile production technology under principles of green chemistry[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4374-4388.
6	孙福曾, 牛保强, 张月成, 等. 山梨醇催化氨化合成腈类化合物[J]. 石油化工, 2018, 47(8): 813-819.
6	SUN Fuzeng, NIU Baoqiang, ZHANG Yuecheng, et al. Synthesis of nitriles from catalytic amination of sorbitol[J]. Petrochemical Technology, 2018, 47(8): 813-819.
7	张弦. 生物质乙醇和丙烯醛制备吡啶碱反应研究[D]. 长沙: 湖南大学, 2013.
7	ZHANG Xian. The research on preparation of pyridine bases from biomass ethanol and acrolein[D]. Changsha: Hunan University, 2013.
8	罗才武, 蒋复量, 李向阳, 等. 3-甲基吡啶合成工艺的研究进展[J].化学工业与工程, 2018, 35(4): 24-31.
8	LUO Caiwu, JIANG Fuliang, LI Xiangyang, et al. Advanced progress in the synthesis of 3-picoline[J]. Chemical Industry and Engineering, 2018, 35(4): 24-31.
9	冯成, 张月成, 赵继全. 乙腈的化学合成研究进展[J]. 现代化工, 2010, 30(2): 29-34.
9	FENG Cheng, ZHANG Yuecheng, ZHAO Jiquan. Advances in synthesis of acetonitrile[J]. Modern Chemical Industry, 2010, 30(2): 29-34.
10	OLIVé G, OLIVé S. Process for preparing acetonitrile: US4179462[P]. 1979-12-18.
11	LAWRENCE J K. Preparation of acetonitrile: US3129241[P]. 1964-04-14.
12	FIERCE W L, LAKE C, SANDNER W J. Preparation of nitriles by catalyzed reaction of alkynes with hydrogen cyanide or cyanogen: US3056826[P]. 1962-10-02.
13	MEUDT A, SCHERER S, BOEHM C. Method for producing nitriles by elimination of water from aldehyde oximes with alkylphosphonic anhydrides: US7405318[P]. 2008-02-07.
14	CALLAHAN J L. A process for manufacture acetonitrile: GB944742[P]. 1963-12-18.
15	KURINA L N, GOLOVKO A K, GALANOY S I, et al. Acetonitrile synthesis method: RU2214396[P]. 2003-10-20.
16	侯雪梅, 闫丽, 张鑫, 等. 固体酸SO₄^2-/ZrO₂-Al₂O₃催化合成乙腈的研究[J]. 吉林师范大学学报(自然科学版), 2009, 30(2): 108-109.
16	HOU Xuemei, YAN Li, ZHANG Xin, et al. Synthesis of acetonitrile catalysted by solid acid SO₄^2-/ZrO₂-Al₂O₃[J]. Journal of Jilin Normal University (Natural Science Edition), 2009, 30(2): 108-109.
17	张华堂, 张英男, 陈静. 乙醇氨氧化法合成高纯度乙腈方法: CN1440963[P]. 2003-09-10.
17	ZHANG Huatang, ZHANG Yingnan, CHEN Jing. Ethanol ammoxidizing process to synthesize high-purity acetonitrile: CN1440963[P]. 2003-09-10.
18	ZHANG Y N, ZHANG Y C, ZHAO J Q, et al. Amination of ethanol to acetonitrile over Ni-doped Co/γ-Al₂O₃ catalyst[J]. Catalysis Communications, 2009, 10(10): 1454-1458.
19	FENG C, ZHANG Y C, ZHAO J Q, et al. Study on alumina-supported cobalt-nickel oxide catalyst for synthesis of acetonitrile from ethanol[J]. Catalysis Letters, 2011, 141(1): 168-177.
20	ZHANG D, ZHANG Y C, ZHAO J Q, et al. Intrinsic kinetics for the synthesis of acetonitrile from ethanol and ammonia over Co-Ni/γ-Al₂O₃ catalyst[J]. Chemical Engineering Research and Design, 2011, 89(10): 2147-2152.
21	张月成, 张頔, 赵继全. Co-Ni/γ-Al₂O₃催化剂上乙醇催化氨化合成乙腈反应的本征动力学[J]. 化工学报, 2011, 62(11): 3156-3163.
21	ZHANG Yuecheng, ZHANG Di, ZHAO Jiquan. Intrinsic kinetics for amination of ethanol to acetonitrile over Co-Ni/γ-Al₂O₃Catalysis[J]. CIESC Journal, 2011, 62(11): 3156-3163.
22	冯成，郭锋，赵继全,等催化丁醇氨化合成丁腈催化剂及工艺的研究[J]. 精细化工, 2010, 27(6): 567-571.
22	FENG Cheng, GUO Feng, ZHAO Jiquan, et al. Study on catalyst and process for the synthesis of butyronitriles through catalytic ammoniation of butanols[J]. Fine Chemicals, 2010, 27(6): 567-571.
23	HU Y F, JIN S H, ZHANG Z C, et al. One-step synthesis of nitriles by the dehydrogenation-amination of fatty primary alcohols over Cu/m-ZrO₂[J]. Catalysis Communication, 2014, 54: 45-49.
24	SHIN C H, JEONG Y S, AN S H. Selective synthesis of acetonitrile by reaction of ethanol with ammonia over Ni/Al₂O₃ catalyst[J]. Korean Journal of Chemical Engineering, 2019, 36(7): 1051-1056.
25	REDDY B M, MANOHAR B. One step synthesis of acetonitrile from ethanol via ammoxidation over Sb-V-P-O/Al₂O₃ catalyst[J]. Journal of the Chemical Society, Chemical Communications, 1993, 24(24): 234-235.
26	FOLCO F. Catalytic processes for the transformation of ethanol into acetonitrile[D]. Bologna, Italy: University of Bologna, 2013.
27	FOLCO F, OCHOA J V, CAVANI F, et al. Ethanol gas-phase ammoxidation to acetonitrile: the reactivity of supported vanadium oxide catalysts[J]. Catalysis Science & Technology, 2016, 7(1):200-212.
28	KATRYNIOK B, PAUL S, DUMEIGNIL F. Recent developments in the field of catalytic dehydration of glycerol to acrolein[J]. ACS Catalysis, 2013, 3(8): 1819-1834.
29	ZHANG Y C, MA T Q, ZHAO J Q. Study on the conversion of glycerol to nitriles over a Fe_19.2K_0.2/γ-Al₂O₃ catalyst[J]. Journal of Catalysis, 2014, 313: 92-103.
30	ARCEO E, MARSDEN P, BERGMAN R G, et al. An efficient didehydroxylation method for the biomass-derived polyols glycerol and erythritol. mechanistic studies of a formic acid-mediated deoxygenation[J]. Chemical Communications, 2009, 23(23): 3357-3359.
31	Li X K, ZHANG Y G. Highly Efficient process for the conversion of glycerol to acrylic acid via gas phase catalytic oxidation of an allyl alcohol intermediate[J]. ACS Catalysis, 2015, 6: 143-150.
32	ZHANG Y C, WEI T Y, ZHAO J Q. Amination of allyl alcohol to propionitrile over a Zn₃₀Cr_4.5/γ-Al₂O₃ bimetallic catalyst via coupled dehydrogenation-hydrogenation reactions[J]. Applied Catalysis A: General, 2013, 467:154-162.
33	ZHANG Y C, SUN F Z, ZHAO J Q, et al. Synthesis of nitriles from allyl alcohol derived from glycerol over a bimetallic catalyst Zn₃₀Ru_1.0/γ-Al₂O₃[J]. Industrial and Engineering Chemistry Research, 2018, 57(13): 4553-4561.
34	CHICHIBABIN A E, OPARINA M P. über die synthese des pyridins aus aldehyden und ammoniak[J]. Journal Für Praktische Chemie, 1924, 107: 154-158.
35	颜翔. 甘油催化氨化合成吡啶碱反应的研究[D]. 天津: 河北工业大学, 2016.
35	YAN Xiang. Study on the catalytic amination of glycerol to pyridine bases[D]. Tianjin: Hebei University of Technology, 2016.
36	冯成, 文彦珑, 赵继全, 等. 乙醇催化氨化合成2-甲基吡啶和4-甲基吡啶[J]. 石油化工， 2010, 39(7): 775-781.
36	FENG Cheng, WEN Yanlong, ZHAO Jiquan, et al. Synthesis of 2-picoline and 4-picoline by catalytic amination of ethanol[J]. Petrochemical Technology, 2010, 39(7): 775-781.
37	文彦珑, 徐卫华, 赵继全, 等. 多金属ZSM-5催化剂的制备及其催化氨化合成2,6-二甲基吡啶[J]. 催化学报, 2011, 32(1): 172-178.
37	WEN Yanlong, XU Weihua, ZHAO Jiquan, et al. Preparation of polymetallic ZSM-5 catalysts and their catalytic performance for 2,6-lutidine synthesis[J]. Chinese Journal of Catalysis, 2011, 32(1): 172-178.
38	VANDERGAAG F J, LOUTER F, VANBEKKUM H. Reaction of ethanol and ammonia to pyridine over ZSM-5-type zeolites[J]. Studies in Surface Science and Catalysis, 1986, 28(1): 763-769.
39	刘娟娟. ZSM-5催化剂上醇氨反应制备吡啶碱研究[D]. 长沙: 湖南大学, 2012.
39	LIU Juanjuan. Studies on synthesis of pyridine bases from ethanol and ammonia over the ZSM-5 catalysts[D]. Changsha: Hunan University, 2012.
40	马天奇, 魏天宇, 赵继全, 等. 丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能[J]. 化工学报, 2014, 65(3): 905-911.
40	MA Tianqi, WEI Tianyu, ZHAO Jiquan, et al. Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline[J]. CIESC Journal, 2014, 65(3): 905-911.
41	ZHANG Y C, YAN X, NIU B Q, et al. A study on the conversion of glycerol to pyridine bases over Cu/HZSM-5 catalysts[J]. Green Chemistry, 2016,18: 3139-3151.
42	XU L J, HAN Z, YAO Q, et al. Towards the sustainable production of pyridines via thermo-catalytic conversion of glycerol with ammonia over zeolite catalysts[J]. Green Chemistry, 2015, 17: 2426-2435.
43	CALVIN J R, DAVIS R D, MCATEER C H. Mechanistic investigation of the catalyzed vapor-phase formation of pyridine and quinoline bases using ¹³CH₂O, ¹³CH₃OH, and deuterium-labeled aldehydes[J]. Applied Catalysis A: General, 2005, 285(1/2): 1-23.
44	HIGASHIO Y, SHOJI T. Heterocyclic compounds such as pyrrole, pyridines, pyrrolidine, piperidine, indole, imidazol and pyrazines[J]. Applied Catalysis A: General, 2004, 260(2): 251-259
45	ZHOU S S, LIU S H, WEI Y F, et al. Coupled fluidized bed reactor for pyridine synthesis[J].Industrial and Engineering Chemistry Research, 2018, 57(22): 7466-7475.
46	ZHANG Y C, ZHANG W Y, ZHAO J Q, et al. Continuous two-step catalytic conversion of glycerol to pyridine bases in high yield[J]. Catalysis Today, 2019, 319: 220-228.
47	ZHANG W Y, DUAN S B, ZHANG Y C. Enhanced selectivity in the conversion of acrolein to 3-picoline over bimetallic catalyst 4.6% Cu-1.0% Ru/HZSM-5(38) with hydrogen as carrier gas[J]. Reaction Kinetics, Mechanisms and Catalysis, 2019, 127(1): 391-411.
48	ZHANG Y C, ZHAI X, ZHAO J Q, et al. Enhanced selectivity in the conversion of glycerol to pyridine bases over HZSM-5/11 intergrowth zeolite[J]. RSC Advances, 2017, 7(38): 23647-23656.
49	LUO C W, CHAO Z S. Unsaturated aldehydes: a novel route for the synthesis of pyridine and 3-picoline[J]. RSC Advances, 2015, 5: 54090-54101.
50	LUO C W, LI A. Synthesis of 3-picoline from acrolein dimethyl acetal and ammonia over NH₄F-HF treated ZSM-5[J]. Reaction Kinetics, Mechanisms and Catalysis, 2018, 125(1): 365-380.

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