负载型Co基双功能催化剂上戊酸酯生物燃料的制备

doi:10.11949/0438-1157.20211319

化工学报 ›› 2022, Vol. 73 ›› Issue (2): 689-698.DOI: 10.11949/0438-1157.20211319

• 催化、动力学与反应器 • 上一篇下一篇

负载型Co基双功能催化剂上戊酸酯生物燃料的制备

王吴玉^1,³(),史玉竹^1,³,严龙¹,张兴华²,马隆龙²,张琦²()

^1.中国科学院广州能源研究所，中国科学院可再生能源重点实验室，广东广州 510640
^2.东南大学能源与环境学院，能源热转换及其过程测控教育部重点实验室，江苏南京 210096
^3.中国科学技术大学纳米科学技术学院，江苏苏州 215123

收稿日期:2021-09-10 修回日期:2021-11-29 出版日期:2022-02-05 发布日期:2022-02-18
通讯作者: 张琦
作者简介:王吴玉（1997—），男，硕士研究生，wwy97@mail.ustc.edu.cn
基金资助:
国家自然科学基金面上项目(51876209);国家重点研发计划项目(2019YFD1100601);中科院战略先导科技专项A类课题(XDA21060102);“广东特支计划”创新领军人才项目(2019TX05l362);广东省“珠江人才计划”本土创新科研团队项目(2017BT01N092);广东省基础与应用基础研究基金项目(2020A1515011540)

Synthesis of valerate biofuels on supported Co-based bifunctional catalysts

Wuyu WANG^1,³(),Yuzhu SHI^1,³,Long YAN¹,Xinghua ZHANG²,Longlong MA²,Qi ZHANG²()

^1.Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.Key Laboratory of Energy Thermal Conversion and Process Measurement and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
^3.Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu, China

Received:2021-09-10 Revised:2021-11-29 Online:2022-02-05 Published:2022-02-18
Contact: Qi ZHANG

摘要/Abstract

摘要：

采用浸渍法制备了HZSM-5、HY、Hβ以及MCM-22四种载体上负载Co的催化剂，在高压反应釜中，开展了以乙酰丙酸乙酯为原料一步法加氢脱氧合成戊酸乙酯以及戊酸生物燃料的研究。采用XRD、XPS、TEM、FT-IR、NH₃-TPD、H₂-TPR、py-FTIR、ICP-AES等对催化剂进行表征。结果表明，10Co/HZSM-5催化剂由于Co在HZSM-5上分布均匀，并且B酸酸性、总酸量以及还原性能最优，在保持较高的反应性能的同时，提高了产物的选择性，具有较高的催化性能。进一步对反应温度、反应压力等进行优化，在反应温度为240℃、压力为3 MPa、反应3 h时，以正辛烷作溶剂，催化剂表现出较高的催化性能，乙酰丙酸乙酯的转化率达到100%，戊酸酯和戊酸的总收率可达90%。

关键词: 乙酰丙酸乙酯, 生物燃料, 加氢脱氧, 钴基催化剂, 分子筛

Abstract:

Four types of Co-supported catalysts, HZSM-5, HY, Hβ and MCM-22, were prepared by the impregnation method. In the high-pressure reactor, the prepared catalyst is used as a raw material for one-step hydrodeoxygenation of ethyl levulinate to synthesize ethyl valerate and valeric acid biofuel. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier infrared (FT-IR), NH₃-TPD, H₂-TPR, py-FTIR, ICP-AES and other technologies are used for catalyst characterization. The results show that, because Co is uniformly distributed on HZSM-5, B acidity, total acidity and reduction performance are the best, while maintaining high reactivity, it improves the selectivity of the product. Therefore, the 10Co/HZSM-5 catalyst has higher catalytic performance. The reaction temperature, reaction pressure, etc. are further optimized. When the reaction temperature is 240℃, the pressure is 3 MPa, and the reaction is 3 h, with n-octane as the solvent, the catalyst shows higher catalytic performance, and the conversion rate of ethyl levulinate reaches 100%, the total yield of valerate and valeric acid can reach 90%.

Key words: ethyl levulinate, biofuel, hydrodeoxygenation, cobalt-based catalyst, molecular sieves

中图分类号:

TK 6

王吴玉, 史玉竹, 严龙, 张兴华, 马隆龙, 张琦. 负载型Co基双功能催化剂上戊酸酯生物燃料的制备[J]. 化工学报, 2022, 73(2): 689-698.

Wuyu WANG, Yuzhu SHI, Long YAN, Xinghua ZHANG, Longlong MA, Qi ZHANG. Synthesis of valerate biofuels on supported Co-based bifunctional catalysts[J]. CIESC Journal, 2022, 73(2): 689-698.

图/表 13

图1 EL转化为EP与PA的反应路径

Fig.1 The reaction path of the conversion of EL to EP and PA

表1 催化剂载体对EL转化的影响

Table 1 The conversion of EL over catalyst with different supports

Catalyst	Si/Al molar ratio	Conversion/%	Yield(C molar fraction)/%
Catalyst	Si/Al molar ratio	Conversion/%	GVL	PA	EP
10Co/HZSM-5	21	98.70	41.91	12.97	20.32
10Co/Hβ	25	97.65	55.95	8.52	16.29
10Co/MCM-22	30	92.37	57.72	8.67	12.80
10Co/HY	26	90.06	62.28	6.34	10.96

图2 不同载体的Co基催化剂的XRD谱图

Fig.2 XRD patterns of Co-based catalysts with different supports

图3 不同载体催化剂的Co 2p能谱

Fig.3 XPS spectra of the catalyst with different support around the Co 2p

图4 不同载体催化剂的TEM与HZSM-5载体的EDX图

Fig.4 TEM of different supported catalysts, EDX image of HZSM-5 as the carrier

图5 不同载体催化剂的H2-TPR谱图

Fig.5 H2-TPR patterns of catalysts with different support

图6 不同载体催化剂的NH3-TPD谱图

Fig.6 NH3-TPD images of cobalt-based catalysts with different support

表2 NH3-TPD测定的弱酸酸量分布情况

Table 2 The distribution of weak acids determined by NH3-TPD

催化剂	温度区间/℃	峰顶温度/℃	酸量/(μmol/g)
10Co/HZSM-5	100~390	242	771
10Co/Hβ	100~410	231	579
10Co/MCM-22	100~390	239	711
10Co/HY	100~450	231	421

表3 NH3-TPD测定的强酸酸量分布情况

Table 3 The distribution of strong acids measured by NH3-TPD

催化剂	温度区间/℃	峰顶温度/℃	酸量/(μmol/g)
10Co/HZSM-5	390~650	491	623
10Co/Hβ	410~650	494	504
10Co/MCM-22	390~600	456	339
10Co/HY	450~600	531	130

图7 不同载体催化剂的py-FTIR谱图

Fig.7 py-FTIR image of different supported catalysts

表4 金属负载量对EL转化的影响

Table 4 The conversion of EL over catalyst with different metal loading.

Catalyst	Conversion/%	Yield (C mole fraction)/%
Catalyst	Conversion/%	GVL	PA	EP	LA（乙酰丙酸）
5Co/HZSM-5	86.57	55.46	9.00	10.39	—
10Co/HZSM-5	98.70	41.91	12.97	20.32	—
15Co/HZSM-5	96.74	42.46	11.39	20.72	—

图8 不同因素对于反应的影响

Fig.8 The influence of different factors on the response

表5 催化剂循环实验

Table 5 Cyclic experiment of catalyst 10Co/HZSM-5

Cycle	Yield/%			Conversion /%
Cycle	EP	PA	GVL	Conversion /%
1	57.38	33.32	—	99
2	55.58	31.54	—	99
3	55.82	29.74	—	97
4	50.38	29.32	5.69	86.3
5	46.66	24.44	8.72	84.27
6	56.24	32.34	—	97
7	55.48	32.11	—	99

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负载型Co基双功能催化剂上戊酸酯生物燃料的制备

Synthesis of valerate biofuels on supported Co-based bifunctional catalysts

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