Co/Al<sub>2</sub>O<sub>3</sub>催化褐煤衍生模型化合物的加氢脱氧制单体烃类化合物

赵云鹏; 司兴刚; 赵薇; 曹景沛; 魏贤勇

doi:10.19906/j.cnki.JFCT.2021032

Co/Al₂O₃催化褐煤衍生模型化合物的加氢脱氧制单体烃类化合物

doi: 10.19906/j.cnki.JFCT.2021032

赵云鹏^{1, 2, ,},
司兴刚¹,
赵薇¹,
曹景沛^1, ,,
魏贤勇^{1, 2}

1.
中国矿业大学煤炭加工与高效利用教育部重点实验室，江苏徐州 221116
2.
新疆大学化工学院新疆维吾尔自治区煤炭清洁转化与化工过程重点实验室，新疆乌鲁木齐 830046

基金项目: 国家自然科学基金(21878325)，中央高校基本科研业务费(中国矿业大学，2019XKQYMS49)和江苏省高校优势学科项目资助

详细信息

通讯作者:
E-mail: zhaoyp@cumt.edu.cn

caojingpei@cumt.edu.cn

中图分类号: TQ530
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出版历程
- 收稿日期: 2020-09-25
- 修回日期: 2020-10-22
- 刊出日期: 2021-02-08

Catalytic hydrodeoxygenation of lignite-derived model compounds to monomeric hydrocarbons over Co/Al₂O₃

ZHAO Yun-peng^{1, 2
, ,},
SI Xing-gang¹,
ZHAO Wei¹,
CAO Jing-pei^{1
, ,},
WEI Xian-yong^{1, 2}

1.
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou 221116, China
2.
Key Laboratory of Coal Clean Conversion & Chemical Engineering Process of Xinjiang Uygur Autonomous Region, College of Chemical Engineering, Xinjiang University, Urumqi 830046, China

Funds: The project was supported by the National Natural Science Foundation of China (21878325), the Fundamental Research Funds for the Central Universities (China University of Mining and Technology, 2019XKQYMS49) and the Priority Academic Program Development of Jiangsu Higher Education Institutions

摘要

摘要: 以钴铝类水滑石(CoAl-LDH)为前驱体，经焙烧和氢气还原制备了Co/Al₂O₃催化剂。采用X 射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等表征手段研究了前驱体及催化剂的理化性质。以2-萘基醚为褐煤模型化合物，考察了Co/Al₂O₃催化其加氢脱氧制单体烃的性能。结果表明，Co/Al₂O₃-700催化剂具有最高的加氢脱氧活性，在温度250 ℃和氢气压力2 MPa反应条件下，反应90 min时2-萘基醚完全转化为单体烃(十氢化萘和四氢化萘)。2-萘基醚先加氢生成6,6′-氧代二(1,2,3,4-四氢萘)，然后断裂C−O键生成四氢化萘和5,6,7,8-四氢-2-萘酚是主要反应路径。此外，Co/Al₂O₃-700对褐煤衍生苄醚和苯醚模型化合物加氢脱氧同样具有很高的催化活性。
- Co/Al₂O₃催化剂 /
- 加氢脱氧 /
- 褐煤衍生模型化合物 /
- 单体烃类化合物
Abstract: A Co/Al₂O₃ catalyst was synthesized by facile calcination and hydrogen reduction of a cobalt-aluminum hydrotalcite CoAl-LDH, and the X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photon spectroscopy (XPS) were used to characterize the physical and chemical properties of the precursor and catalysts. Using 2-naphthyl ether as the lignite derived model compound, the catalytic performance of Co/Al₂O₃ on the hydrodeoxygenation of 2-naphthyl ether to monomeric hydrocarbons was investigated. The results show that Co/Al₂O₃-700 has the highest hydrodeoxygenation activity. Under the conditions of 250 ℃, 2 MPa of initial H₂ pressure and90 min of holding time, the 2-naphthyl ether is completely converted to monomeric hydrocarbons (decalin and tetralin), in which the 2-naphthyl ether is first converted to 6,6'-oxybis (1,2,3,4-tetrahydronaphthalene) by hydrogenation and then the tetralin and 5,6,7,8-tetrahydronaphthalene-2-naphthol are formed by the cleavage of C−O bond. In addition, Co/Al₂O₃-700 also shows high activity for the hydrodeoxygenation of lignite-derived benzyl ether and phenyl ether model compounds.
- Co/Al₂O₃ catalyst /
- hydrodeoxygenation /
- lignite-derived model compounds /
- monomeric hydrocarbons

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图 1 CoAl-LDH、Co₃O₄/Al₂O₃和Co/Al₂O₃-700的XRD谱图

Figure 1 XRD patterns of CoAl-LDH, Co₃O₄/Al₂O₃ and Co/Al₂O₃-700

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图 2 CoAl-LDH的TG曲线(a)和Co₃O₄/Al₂O₃的H₂-TPR曲线(b)

Figure 2 TG curve of CoAl-LDH (a) and H₂-TPR profile of Co₃O₄/Al₂O₃ (b)

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图 3 CoAl-LDH和Co₃O₄/Al₂O₃的扫描电镜((a)和(b))、透射电镜((c)和(d))照片

Figure 3 SEM ((a) and (b)) and TEM ((c) and (d)) images of the CoAl-LDH and Co₃O₄/Al₂O₃

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图 4 Co/Al₂O₃-700的扫描电镜及元素面分布照片

Figure 4 SEM and EDS mapping images of Co/Al₂O₃-700

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图 5 CoAl-LDH、Co₃O₄/Al₂O₃和Co/Al₂O₃-700的N₂吸附-脱附等温线(a)和孔径分布曲线(b)

Figure 5 N₂ adsorption-desorption isotherms (a) and the pore size distribution curves of CoAl-LDH, Co₃O₄/Al₂O₃ and Co/Al₂O₃-700 (b)

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图 6 Co/Al₂O₃-700的XPS光谱谱图

Figure 6 XPS spectra of Co/Al₂O₃-700

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图 7 反应温度(a)氢气压力(b)和反应时间(c)对于2-萘醚转化的影响

Figure 7 Effects of temperature (a), hydrogen pressure (b) and time (c) on 2-naphthyl ether conversion reaction conditions: 50 mg 2-naphthyl ether, 25 mg Co/Al₂O₃-700, 2 MPa H₂, 2 h (a); 50 mg 2-naphthyl ether, 25 mg Co/Al₂O₃-700, 250 ℃, 2 h (b); 50 mg 2-naphthyl ether, 25 mg Co/Al₂O₃-700, 250 ℃, 2 MPa H₂ (c)

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图 8 Co/Al₂O₃-700催化2-萘基醚加氢脱氧可能的反应路径

Figure 8 Possible reaction pathways of 2-naphthyl ether hydrodeoxygenation over Co/Al₂O₃-700

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图 9 Co/Al₂O₃-700催化2-萘基醚加氢脱氧的稳定性测试

Figure 9 Stability test of Co/Al₂O₃-700 in hydrodeoxygenation of 2-naphthyl ether

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表 1 CoAl-LDH、Co₃O₄/Al₂O₃和Co/Al₂O₃-700的物理性质

Table 1 Textural property of CoAl-LDH, Co₃O₄/Al₂O₃ and Co/Al₂O₃-700

Sample	Surface area A/ (m²·g⁻¹)^a	Pore volume v/ (cm³·g⁻¹)^b	Pore diameter d/nm^b	Cobalt content w/%^c
CoAl-LDH	67.46	0.39	3.83	32.5
Co₃O₄/Al₂O₃	132.16	0.24	3.41	49.8
Co/Al₂O₃-700	71.97	0.48	3.82	57.5
^a calculated by the BET method; ^b calculated by the BJH method; ^c measured with LA-ICP-MS

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表 2 还原温度对催化剂催化2-萘基醚加氢脱氧的影响

Table 2 Effect of catalyst reduction temperature (RT) on the hydrodeoxygenation of 2-naphthyl ether

Entry	RT/°C	Conv./%	Product selectivity /%
Entry	RT/°C	Conv./%
1	600	68.3	10.2	62.1	11.4	7.8	2.7	5.8
2	700	87.6	10.5	64.2	17.9	2.7	1.2	3.5
3	800	84.5	7.8	60.7	19.5	5.0	1.9	5.1
reaction conditions: 50 mg 2-naphthyl ether, 25 mg Co/Al₂O₃-t, 15 mL n-hexane, 2 MPa H₂, 230°C, 120 min

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表 3 2-萘基醚及其加氢产物中C-O键的解离能

Table 3 The BDE of C-O bonds in 2-naphthyl ether and its hydrogenation products

Compound
BDE/ (kJ·mol⁻¹)	344.7	344.3	347.4	333.7

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