不同方法合成钼基氧硫复合物催化剂及其合成气制乙醇性能研究

宇文晓萌; 冯文爽; 穆晓亮; 赵璐; 房克功

doi:10.19906/j.cnki.JFCT.2024027

不同方法合成钼基氧硫复合物催化剂及其合成气制乙醇性能研究

doi: 10.19906/j.cnki.JFCT.2024027

宇文晓萌^{1, 2,},
冯文爽^{1, 2,},
穆晓亮^1,,
赵璐^1, ,,
房克功^1, ,

1.
中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目: 国家重点研发计划（2023YFB4103201），国家自然科学基金（21978313），中国科学院山西煤炭化学研究所创新基金（SCJC–DT–2022–05），煤转化国家重点实验室自主研究课题项目（2020BWZ002），中国科学院青年创新促进会人才项目（2020181）资助

详细信息

通讯作者:
Tel: +86-0351-4041153, E-mail: zhaolu@sxicc.ac.cn

kgfang@sxicc.ac.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2024-04-09
- 修回日期: 2024-04-26
- 录用日期: 2024-04-26
- 网络出版日期: 2024-06-04

Study on different synthesis methods of molybdenum-based oxide and sulfide catalyst and its performance in syngas to ethanol

YUWEN Xiaomeng^{1, 2
,},
FENG Wenshuang^{1, 2
,},
MU Xiaoliang^1
,,
ZHAO Lu^{1
, ,},
FANG Kegong^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Key Research and Development Program of China (2023YFB4103201), National Natural Science Foundation of China (21978313), the Innovation Foundation of ICC-CAS (SCJC-DT-2022-05), the Autonomous Research Project of SKLCC (2020BWZ002) and the Youth Innovation Promotion Association of CAS (2020181).

摘要

摘要: 合成气一步制乙醇是利用非石油资源生产乙醇的重要方法，如何提高乙醇选择性、创制高效催化剂是改善过程经济性的重点。本研究从硫化钼前体出发，分别采用传统热法和射频低温等离子体法制备钼基氧硫复合物催化剂并考察其催化合成气制乙醇反应性能。利用XRD、UV-visible、HR-TEM、SEM、HAADF-STEM、XPS、CO-TPD、H₂-TPD、CO₂-TPD和In-situ DRIFTS等表征手段研究不同制备方法下合成的钼基氧硫复合物催化剂的不同物化性质，进而探究特征差异引发的催化反应性能变化。其中，MOS-P催化剂表现出最佳性能，在6 MPa、320 ℃、空速4500 h⁻¹的反应条件下，CO转化率达到22.5%，总醇选择性可达71.4%，其中，总醇中乙醇占比为29.1%。有关研究将为合成气定向转化提供理论指导并为新型钼基材料的设计与制备提供借鉴。
- 合成气 /
- CO加氢 /
- 乙醇 /
- 钼基氧硫复合物 /
- 射频低温等离子体
Abstract: Ethanol is a significant chemical feedstock, which can be employed not only as a raw material for chemicals and polymers, but also as an additive to petrol. It is typically produced in industry through either fermentation or ethylene hydration. In light of the growing demand for ethanol, it is imperative to investigate the potential of multi-channel production of ethanol. One-step ethanol production from syngas represents a significant method of ethanol production from non-fossil oil energy sources, and it is also an important means of clean utilization of coal. The cost of direct ethanol production from syngas is relatively low, but the distribution of alcohols with different carbon numbers in the alcohol product is wide, which makes subsequent separation difficult and restricts its large-scale development. Consequently, in the research of direct ethanol production from syngas, the key points to improve the process economics and promote the development of this technology are to improve the selectivity of ethanol and develop the efficient catalysts. Mo-based catalysts can be employed for low-hydrogen syngas. At the same time, it is challenging to deposit carbon, exhibits robust resistance to sulfur poisoning, and demonstrates excellent stability, which also extends the reaction cycle. However, the methanol content of the alcohol product is relatively high. Although the use of Fischer-Tropsch element modification can significantly reduce the methanol selectivity, it will inevitably lead to the problem of broadening the distribution of alcohols. In recent years, there has been a growing attention in the preparation of catalysts using non-thermal plasma technology. Non-thermal plasma comprises not only electrons, ions, molecules and free radicals, but also photons and excited substances. Previous studies have demonstrated that the non-thermal plasma method can induce alterations in the nucleation of the active phase and the crystal growth mode in the preparation of catalysts. Concurrently, for thermodynamically unfavorable reactions, the utilization of non-thermal plasma technology can disrupt the thermodynamic equilibrium limit, thereby facilitating the reaction. In this study, Mo-based oxide and sulfide composite catalysts were prepared from the precursor of molybdenum sulfide by two distinct methods: the conventional thermal method and the RF non-thermal plasma method. The catalytic performance of Mo-based oxide and sulfide composite catalysts for the synthesis of ethanol from syngas was then investigated. A range of analytical techniques were employed to investigate the physical and chemical properties of the molybdenum-based oxygen-sulfur complex catalysts synthesized by different preparation methods. These included XRD, UV-visible, HR-TEM, SEM, HAADF-STEM, XPS, CO-TPD, H₂-TPD, CO₂-TPD and In-situ DRIFTS. Moreover, the objective was also to ascertain the impact of the physical and chemical properties on the catalytic performance of the different catalysts. Among them, the MOS-P catalyst exhibited the best catalytic performance. Under the reaction conditions of 6 MPa, 320 ℃, and a space velocity of 4500 h⁻¹, the CO conversion reached 22.5%. The selectivity of total alcohols was 71.4%, with ethanol accounting for 29.1% of the total alcohols. This research will provide theoretical guidance for the directional conversion of syngas and serves as a reference for the design and preparation of new molybdenum-based materials.
- syngas /
- CO hydrogenation /
- ethanol /
- molybdenum-based oxide and sulfide /
- RF non-thermal plasma

HTML全文

图 1 射频低温等离子体装置示意图

Figure 1 Schematic diagram of radio frequency non-thermal plasma device

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图 2 合成气制乙醇反应流程示意图

Figure 2 Schematic diagram of reaction device for alcohols synthesis from syngas

1: Reagent gas; 2: Pre-system pressure setter; 3: Mass flowmeter; 4: Temperature controller; 5: Heating furnace;6: Reactor; 7: Catalytic bed; 8: Heat trap; 9: Cold trap;10: Post-system pressure setter; 11: Gas chromatography;12: Gas outlet.

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图 3 不同方法合成的Mo基氧硫复合物催化剂的XRD谱图（a）和UV-visible谱图（b）

Figure 3 XRD patterns (a) and UV-visible profiles (b) of the different MOS catalysts synthesized by different methods

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图 4 不同催化剂中MoS₂与MoO₃的相对含量

Figure 4 The relative content of MoS₂ and MoO₃ in different catalysts

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图 5 （a）MS催化剂的SEM图像；（b）MS催化剂的HR-TEM图像；（c）MOS-T催化剂的SEM图像；（d）MOS-T催化剂的HR-TEM图像；（e）MOS-P催化剂的SEM图像；（f）MOS-P催化剂的HR-TEM图像；（g）MO催化剂的SEM图像；（h）MO催化剂的HR-TEM图像；（i）−（n）各催化剂中MoS₂和MoO₃的平均粒径

Figure 5 (a) SEM image of the MS catalyst; (b) HR-TEM image of the MS catalyst; (c) SEM image of the MOS-T catalyst; (d) HR-TEM image of the MOS-T catalyst; (e) SEM image of the MOS-P catalyst; (f) HR-TEM image of the MOS-P catalyst; (g) SEM image of the MO catalyst; (h) HR-TEM image of the MO catalyst; (i)−(n) Particle size of MoS₂ and MoO₃ in each catalyst

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图 6 （a）、（b）MOS-P催化剂的TEM图像；（c）MOS-P催化剂的HAADF-STEM图像

Figure 6 (a), (b) TEM images of the MOS-P catalyst; (c) HAADF-STEM images of the MOS-P catalyst

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图 7 不同催化剂的XPS光谱谱图

Figure 7 XPS spectra of different catalysts

(a): Full spectrum scanning results; (b): Mo element; (c): O element; (d): S element.

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图 8 不同催化剂的CO-TPD谱图

Figure 8 CO-TPD profiles of the different catalysts

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图 9 不同催化剂的H₂-TPD谱图

Figure 9 H₂-TPD profiles of the different catalysts

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图 10 不同催化剂的CO₂-TPD谱图

Figure 10 CO₂-TPD profiles of the different catalysts

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图 11 MOS-T催化剂与MOS-P催化剂的in-situ DRIFTS谱图

Figure 11 In-situ DRIFTS over the MOS-T catalyst and MOS-P catalyst

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表 1 不同催化剂的CO、H₂和CO₂吸附量

Table 1 Amount of CO, H₂ and CO₂ on different catalysts

Catalyst	Amount of CO/(μmol·g⁻¹)	Amount of H₂/(μmol·g⁻¹)			Amount of CO₂/(μmol·g⁻¹)
Catalyst	Amount of CO/(μmol·g⁻¹)	peak i	peak ii	total	Amount of CO₂/(μmol·g⁻¹)
MS	39	−	28	28	376
MOS-T	47	116（60%）	78（40%）	194	352
MOS-P	80	90（45%）	111（55%）	201	294
MO	21	−	10	10	−

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表 2 不同催化剂的合成气制乙醇催化反应性能^a

Table 2 The catalytic performance of different catalysts for the synthesis of ethanol from syngas ^a

Catalyst	CO conv./%	STY_EtOH /(mg·mL⁻¹·h⁻¹)	Product selectivity s/% ^b		Alcohol distribution w/%			Hydrocarbon distribution w/%
Catalyst	CO conv./%	STY_EtOH /(mg·mL⁻¹·h⁻¹)	ROH^c	CH_n^d	MeOH	EtOH	C₃₊OH^e	C₁	C₂	C₃₊
MS	14.1	13.5	68.8	31.2	66.5	22.5	11.0	57.2	26.1	16.7
MOS-T	18.9	18.9	69.6	30.4	64.3	23.6	12.1	55.3	27.7	17.0
MOS-P	22.5	32.0	71.4	28.6	55.2	29.1	15.7	62.5	23.1	14.4
MO	12.3	14.2	55.9	44.1	53.6	28.3	18.1	61.2	24.2	14.6
^a: Reactions were carried out at 320 ℃, 6.0 MPa, GHSV=4500 h⁻¹, H₂/CO =2. STY is space-time yield; ^b: CO₂ free; ^c: ROH means total alcohols and ^d: CH_n means total hydrocarbons; ^e: Alcohols with carbon number above 3 were obtained in the product (propanol, butanol and pentanol).

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表 3 本研究与文献中合成乙醇Mo基催化剂的催化性能对比

Table 3 A comparison of the catalytic performance of Mo-based catalysts for ethanol synthesis between this study and the literature

Catalyst	A^[22] Rh-K-MoP/SiO₂	B^[25] MoO₂-Pla	C^[52] β-Mo₂C	D^[53] K/β-Mo₂C/GMC	E^[54] Mo-K/MWCNT	This work MOS-P
CO conversion/%	18.0	16.3	58.6	1.3	19	22.5
EtOH/ROH/%	27.7	38.0	18	34.6	28	29.1
STY_EtOH/(mg·mL⁻¹·h⁻¹)	22.8	21.6	2.2	11.5	30.8	32.0

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