K改性NiMoS/ZnAl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

详细信息

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

K-modified NiMoS/ZnAl 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: National Natural Science Foundation of China (21576288)

摘要

摘要: 本研究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β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 C_{2 +} 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 C_{2 +} alcohols.
- NiMoS/ZnAl catalysts /
- K modification /
- synthesis gas /
- higher alcohols /
- synergetic effect.

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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图片和元素面扫

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 result 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	Mo^{4 +}	Mo^{5 +}	Mo^{6 +}	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 /%			C_{2 +}OH STY/mg·g_cat⁻¹·h⁻¹
Catalyst	x_CO /%	alcohols	hydrocarbons	CO₂	C_{2 +}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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