K改性NiMoS/ZnAl氧化物负载型催化剂合成气制低碳醇性能研究

曹轶华; 张鑫; 阴雪利; 甘永豪; 代小平

doi:10.19906/j.cnki.JFCT.2023036

K改性NiMoS/ZnAl氧化物负载型催化剂合成气制低碳醇性能研究

doi: 10.19906/j.cnki.JFCT.2023036

中国石油大学(北京)化学工程与环境学院重质油国家重点实验室, 北京 102249

基金项目: 国家自然科学基金（21576288）资助

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通讯作者:
Tel: 18911226236, E-mail: daixp@cup.edu.cn

中图分类号: O643
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出版历程
- 收稿日期: 2023-03-20
- 修回日期: 2023-04-18
- 录用日期: 2023-04-18
- 网络出版日期: 2023-05-06
- 刊出日期: 2024-01-09

K-modified NiMoS/ZnAl oxide catalysts for higher alcohols synthesis from syngas

College of Chemical Engineering and Environment, State Key Laboratory of Heavy Oil Processing, China University of Petroleum Changping, Beijing 102249, China

Funds: The project was supported by the National Natural Science Foundation of China (21576288)

摘要

摘要: 采用共沉淀法和浸渍法，以ZnAl混合金属氧化物为载体，制备了系列不同K/Mo物质的量比的高分散K改性NiMoS/ZnAl催化剂，并对其合成气转化制低碳醇性能进行了研究。结果表明，K的引入可以调变MoS₂片层的堆积程度和尺寸，提高NiS_x和NiMoS之间的协同作用，促进低碳醇合成（HAS）过程中CH_x的插入和非解离CO的插入能力，有效抑制烃类和CO₂的生成。其中，K/Mo物质的量比为0.6的KNiMoS/ZnAl催化剂具有最多的双层MoS₂结构（33.7%）和适宜的NiS_x与NiMoS协同作用，产物中总醇选择性达到69.8%，低碳醇空时产率为78.6 mg/(g·h)。
- NiMoS/ZnAl催化剂 /
- K改性 /
- 合成气 /
- 低碳醇 /
- 协同效应
Abstract: Improving the C₂₊ alcohols yield is highly desirable for the direct synthesis of higher alcohols from syngas. In this work, a series of highly dispersed K-modified NiMoS catalysts with different K contents on ZnAl-mixed oxide support were prepared by the combination of co-precipitation and impregnation method. And their performance in higher alcohols synthesis (HAS) from syngas was investigated. The results show that the introduction of K can modulate the stacking degree of MoS₂ slabs, and improve the interaction between NiS_x and NiMoS phases. The as-prepared catalyst is conducive to promote the insertion of CH_x and non-dissociative CO in HAS, and effectively suppress the generation of hydrocarbons and CO₂. The 0.6KNiMoS/ZnAl catalyst exhibits the most double-layer MoS₂ slabs (33.7%) and highly synergetic effects between NiS_x and NiMoS to achieve the total alcohols selectivity (69.8%) and space-time yield (78.6 mg/(g·h)) of C₂₊ alcohols.
- NiMoS/ZnAl catalysts /
- K modification /
- synthesis gas /
- higher alcohols /
- synergetic effect

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FIG. 2877. FIG. 2877.

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图 1 （a）xKNiMoS/ZnAl、（b）KNiMoS/ZnAl-x催化剂的XRD谱图，和（c）xKNiMoS/ZnAl催化剂的Raman光谱谱图

Figure 1 XRD patterns of (a) xKNiMoS/ZnAl catalysts, (b) KNiMoS/ZnAl-x catalysts, and (c) Raman spectra of xKNiMoS/ZnAl catalysts

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图 2 xKNiMoS/ZnAl催化剂的（a）Mo 3d、（b）S 2p和（c）Ni 2p谱图

Figure 2 XPS spectra of (a) Mo 3d, (b) S 2p and (c) Ni 2p for xKNiMoS/ZnAl catalysts

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图 3 xKNiMoS/ZnAl催化剂（x=（a）0，（b）0.3，（c）0.6，（d）1.0）的TEM照片、MoS₂的（e）晶粒堆积层数和（f）长度分布、xKNiMoS/ZnAl催化剂（x=（g）0.3，（h）1.0）的HAADF-STEM图片和元素分布

Figure 3 TEM images of xKNiMoS/ZnAl catalysts (x=(a) 0, (b) 0.3, (c) 0.6, (d) 1.0), (e) MoS₂ stacking degree and (f) MoS₂ slab length, HAADF-STEM images and element mapping of xKNiMoS/ZnAl catalysts (x=(g) 0.3, (h) 1.0)

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图 4 xKNiMoS/ZnAl催化剂的（a）醇分布、（b）烃分布、（c）醇类ASF分布、（d）烃类ASF分布

Figure 4 Carbon distribution of (a) alcohols and (b) hydrocarbons, the ASF distribution of (c) alcohols, and (d) hydrocarbons on xKNiMoS/ZnAl catalysts

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图 5 0.6KNiMoS/ZnAl催化剂100 h稳定性

Figure 5 Stability test of 0.6KNiMoS/ZnAl for 100 h

Reaction conditions: t=350 ℃, p=5 MPa, GHSV=3000 mL/(g·h) and CO/H₂=1.

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图 6 NiS_x和NiMoS双活性位协同增强低碳醇合成示意图

Figure 6 Synergistic promotion effect for HAS by NiS_x and NiMoS dual active sites

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表 1 xKNiMoS/ZnAl催化剂的ICP-OES元素分析

Table 1 ICP-OES results of xKNiMoS/ZnAl catalysts

Sample	UItimate analysis w/%					K/Mo
Sample	K	Ni	Mo	Zn	Al	K/Mo
KNiMoS/ZnAl	0	7.49	12.12	29.20	6.86	0
0.3KNiMoS/ZnAl	1.44	7.27	12.30	28.24	6.60	0.29
0.6KNiMoS/ZnAl	2.98	7.54	12.40	28.16	6.53	0.59
1.0KNiMoS/ZnAl	4.89	7.33	12.29	29.95	6.67	0.98

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表 2 xKNiMoS/ZnAl催化剂的XPS表征

Table 2 XPS characterization of xKNiMoS/ZnAl catalysts

Catalyst	Binding energies for Mo 3d_5/2/eV			Sulfidation degree/%
Catalyst	Mo⁴⁺	Mo⁵⁺	Mo⁶⁺	Sulfidation degree/%
NiMoS/ZnAl	229.0	230.2	232.5	65.6
0.3KNiMoS/ZnAl	229.0	230.2	232.4	53.8
0.6KNiMoS/ZnAl	229.0	230.1	232.3	48.6
1.0KNiMoS/ZnAl	228.9	230.2	232.0	41.8

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表 3 xKNiMoS/ZnAl催化剂HRTEM表征

Table 3 HRTEM characterization of xKNiMoS/ZnAl catalysts

Catalyst	L_average/nm	N_average	ƒ_Mo/%
NiMoS/ZnAl	5.80	2.44	16.7
0.3KNiMoS/ZnAl	5.98	2.64	15.9
0.6KNiMoS/ZnAl	5.96	2.96	16.2
1.0KNiMoS/ZnAl	6.37	3.01	9.2

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表 4 KNiMoS/ZnAl催化剂的HAS性能

Table 4 Catalytic performance of carbon monoxide hydrogenation on KNiMoS/ZnAl catalysts

Catalyst	x_CO/%	Selection s/%			C₂₊OH STY/(mg·g_cat⁻¹·h⁻¹)
Catalyst	x_CO/%	alcohols	hydrocarbons	CO₂	C₂₊OH STY/(mg·g_cat⁻¹·h⁻¹)
NiMoS/ZnAl	12.5	48.3	28.5	23.2	62.4
0.3KNiMoS/ZnAl	12.0	60.4	19.2	20.4	69.1
0.6KNiMoS/ZnAl	11.6	69.8	11.7	18.5	78.6
1.0KNiMoS/ZnAl	10.7	64.9	15.5	19.6	63.9
KNiMoS/ZnAl-60	9.0	63.6	19.2	17.1	53.9
KNiMoS/ZnAl-120	10.7	64.9	15.5	19.6	63.9
KNiMoS/ZnAl-180	8.8	59.0	22.7	18.3	48.8
Reaction conditions: p=5 MPa，t=350 ℃，GHSV=3000 mL/(g·h).

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