Ni-Cu-Ru/HZSM-5催化木质素生物油加氢脱氧制芳香烃的研究

LI Bing-shuo; FENG Bi-xuan; WU Kai-ye; YANG Tian-hua

doi:10.1016/S1872-5813(22)60061-6

Ni-Cu-Ru/HZSM-5催化木质素生物油加氢脱氧制芳香烃的研究

doi: 10.1016/S1872-5813(22)60061-6

沈阳航空航天大学能源与环境学院辽宁省清洁能源重点实验室, 辽宁沈阳110136

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中图分类号: TK6
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出版历程
- 收稿日期: 2022-03-03
- 修回日期: 2022-05-01
- 录用日期: 2022-06-22
- 网络出版日期: 2022-09-15
- 刊出日期: 2023-03-15

Hydrodeoxygenation of lignin derived bio-oil into aromatic hydrocarbons over Ni-Cu-Ru/HZSM-5 catalyst

Shenyang Aerospace University, College of Energy and Environment, Key Laboratory of Clean Energy of Liaoning, Shenyang 110136, China

Funds: The project was supported by the National Natural Science Foundation of China (51906165, 52176195).

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Corresponding author: E-mail: thyang@sau.edu.cn

摘要

摘要: 木质素所得生物油（LDB）成分相对复杂对其后续利用产生巨大挑战。本研究以LDB为原料，在超临界乙醇条件下（320 ℃，14 MPa），以NaOH和负载金属（Ni、Cu和Ru）共同改性的HZSM-5为催化剂制备富含芳香烃的生物油。结果表明，脱硅处理后负载Ni、Cu和Ru三种金属制得的Ni-Cu-Ru/DeHZSM-5催化剂表现出最佳的催化活性，其中，提质油（UBO）中芳香烃的相对含量达到28.95%。此外，结合GC-MS分析结果，提出了愈创木酚、丁香酚和甲基愈创木酚潜在的加氢反应路径。LDB在Ni-Cu-Ru/DeHZSM-5的催化加氢作用下，提质生物油（UBO）的收率可达到80.40%，能量回收率达到96.32%。在催化加氢过程中主要发生了脱甲氧基化反应和脱水反应。相比于LBD，UBO的热值提高了19.80%，达到35.22 MJ/kg，且其含水量、黏度和酸值等性能均有显著改善。具有微介孔结构及Ni、Cu和Ru负载共同修饰的Ni-Cu-Ru/DeHZSM-5催化剂有利于提升芳香烃的收率。
- 木质素 /
- 生物油 /
- 加氢脱氧 /
- 催化剂 /
- 机理 /
- 芳香烃
Abstract: The complexity and diversity of lignin derived bio-oil (LDB) has posed a great challenge to the subsequent processing and utilization. In this work, HZSM-5 was modified by sodium hydroxide and followed by Ni, Cu and Ru species. LDB was used as the raw biocrude to prepare bio-oil rich in aromatic hydrocarbons with modified HZSM-5 catalysts under supercritical ethanol conditions (320 °C, 14 MPa). Results showed that the desilicated HZSM-5 with the loading of Ni, Cu and Ru (Ni-Cu-Ru/DeHZSM-5) exhibited the best catalytic performance with a high relative amount of aromatic hydrocarbons of 28.95%. After catalytic hydrodeoxygenation (HDO) of LDB, 80.40% upgraded bio-oil (UBO) with 96.32% energy recovery was obtained in the presence of Ni-Cu-Ru/DeHZSM-5. Demethoxylation and dehydration were the main reactions in the catalytic HDO process. Potential reaction pathways of guaiacol, syringol and creosol were also proposed in this paper. The heating value of UBO reached 35.22 MJ/kg compared with LDB, which was increased by 19.80%. The water content and viscosity of UBO were also significantly improved. The micro-mesoporous structure of modified HZSM-5 with loading of Ni, Cu and Ru was beneficial to promote the yield of the aromatic hydrocarbons.
- lignin /
- bio-oil /
- hydrodeoxygenation /
- catalyst /
- mechanism /
- aromatic hydrocarbons

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FIG. 2161. FIG. 2161.

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Figure 1 XRD patterns of modified and fresh HZSM-5 catalysts

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Figure 2 SEM images and EDS mapping of modified and fresh HZSM-5 catalysts

(a): HZSM-5; (b): DeHZSM-5; (c): Cu/DeHZSM-5; (d): Ni-Cu/DeHZSM-5; (e): Ni-Cu-Ru/DeHZSM-5

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Figure 3 Products yields from HDO of LDB under different catalytic conditions

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Figure 4 FT-IR spectra of oils obtained under different catalytic conditions

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Figure 5 Compositions of UBO obtained under different catalytic conditions

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Figure 6 Possible reaction pathway for the catalytic HDO of LDB

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Table 1 Textural properties of modified and fresh HZSM-5 catalysts

Catalyst	S_BET / (m²·g⁻¹)	v_meso / (cm³·g⁻¹)	v_micro / (cm³·g⁻¹)	v_total / (cm³·g⁻¹)
HZSM-5	161.24	0.15	0.04	0.19
DeHZSM-5	168.20	0.48	0.02	0.50
Cu/DeHZSM-5	191.85	0.43	0.05	0.48
Ni-Cu/DeHZSM-5	186.85	0.31	0.05	0.36
Ni-Cu-Ru/DeHZSM-5	183.97	0.40	0.04	0.44

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Table 2 Elemental analysis and properties of LDB and UBO

Property	LDB	Blank	UBO
Property	LDB	Blank	HZSM-5	De/HZSM-5	Ni-Cu/DeHZSM-5	Ni-Cu-Ru/DeHZSM-5
C/%	67.12	69.01	73.62	71.99	74.74	76.97
H/%	7.08	7.29	7.91	7.74	7.86	8.16
O^a/%	24.00	22.07	16.79	17.34	15.19	12.72
N/%	1.66	1.45	1.54	2.75	1.97	1.95
S/%	0.14	0.18	0.14	0.18	0.24	0.20
H/C	1.27	1.27	1.29	1.29	1.26	1.27
O/C	0.27	0.24	0.17	0.18	0.15	0.12
HHV^b/(MJ·kg⁻¹)	29.29	30.40	33.33	32.61	33.88	35.28
Water content/%	19.84	16.31	12.17	14.55	7.69	2.73
Viscosity/(mm²·s⁻¹@25 °C)	38.95	35.63	26.71	28.84	20.17	16.82
^a Determined by difference, ^b HHV = 0.3516C + 1.16225H − 0.1109O + 0.0628N + 0.10465S^[21]

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