Fe基催化剂的酸性调控及其对加氢脱硫反应路径选择性的影响

李国省; 李昆鸿; 李晓涵; 尹馨蕊; 邵嘉欣; 郭荣; 任申勇; 郭巧霞; 申宝剑

doi:10.1016/S1872-5813(23)60389-5

Fe基催化剂的酸性调控及其对加氢脱硫反应路径选择性的影响

doi: 10.1016/S1872-5813(23)60389-5

李国省^1,,
李昆鸿^1,,
李晓涵^1,,
尹馨蕊^1,,
邵嘉欣^1,,
郭荣^1,,
任申勇^1,,
郭巧霞^2,,
申宝剑^1, ,

1.
中国石油大学(北京) 化学工程与环境学院重质油全国重点实验室 CNPC催化重点实验室, 北京 102249
2.
中国石油大学(北京) 理学院, 北京 102249)

基金项目: 国家自然科学基金创新研究群体科学基金（22021004）和国家自然科学基金（21776304）资助

详细信息

通讯作者:
Tel: 010-89733369, Fax: 010-89733369, E-mail: baojian@cup.edu.cn

中图分类号: O643.38
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- 被引次数: 0
出版历程
- 收稿日期: 2023-09-05
- 修回日期: 2023-10-09
- 录用日期: 2023-10-10
- 网络出版日期: 2023-10-31

Acidity regulation of Fe-based catalysts and its effect on the selectivity of HDS reaction pathways

LI Guosheng^1
,,
LI Kunhong^1
,,
LI Xiaohan^1
,,
YIN Xinrui^1
,,
SHAO Jiaxin^1
,,
GUO Rong^1
,,
REN Shenyong^1
,,
GUO Qiaoxia^2
,,
SHEN Baojian^{1
, ,}

1.
State Key Laboratory of Heavy Oil Processing; the Key Laboratory of Catalysis of CNPC; College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China
2.
College of Science, China University of Petroleum, Beijing 102249, China

Funds: The project was supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (22021004) and National Natural Science Foundation of China (21776304).

摘要

摘要: 以Fe作为主活性金属、Zn作为助活性金属，制备了Y型分子筛改性的Fe基加氢脱硫（HDS）催化剂。采用低温氮气物理吸附、X射线衍射（XRD）、氢气程序升温还原（H₂-TPR）、氨气程序升温脱附（NH₃-TPD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）和吡啶红外（Py-IR）等表征方法对改性前后Fe基催化剂的形貌、孔结构、分散性、还原性、电子缺陷结构以及酸性等变化进行了研究，并使用固定床反应器对Fe基催化剂的HDS性能进行了评价。结果表明，Y型分子筛的引入提供了Brønsted（B）酸中心，使得Fe基催化剂的脱硫率提高了10.7%−34.1%。同时，B酸中心提高了催化剂的直接脱硫（DDS）反应路径的选择性。此外，B酸中心在促进DDS反应路径选择性增加的同时，抑制了预加氢脱硫（HYD）反应路径中四氢二苯并噻吩（THDBT）和六氢二苯并噻吩（HHDBT）更进一步的深度加氢，从而在保证脱硫率提升的同时又降低了氢耗。其根本原因可能是Y型分子筛的引入增强了催化剂的酸性，特别是B酸中心和活性金属之间的相互作用促进了电子转移，从而调节了Fe物种的电子缺陷结构，进而提升了催化剂的HDS性能。
- Fe基催化剂 /
- 酸性 /
- Y型分子筛 /
- 电子缺陷结构 /
- 加氢脱硫 /
- 二苯并噻吩
Abstract: An Fe-based hydrodesulfurization (HDS) catalyst modified by Y zeolite was developed using Fe as the main active metal and Zn as a promoter. The change of morphology, pore structure, dispersity, reducibility, electronic defect structure and acidity of the Fe-based catalysts before and after modification were investigated using low-temperature nitrogen physical adsorption, X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR), NH₃-temperature programmed desorption (NH₃-TPD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and pyridine infrared spectroscopy (Py-IR). Meanwhile, the HDS performance of the Fe-based catalyst was evaluated using a fixed-bed reactor. The results showed that the introduction of Y zeolite provided the Brønsted (B) acid sites, which increased the sulfur removal rates of Fe based catalysts by 10.7% -34.1%. Meanwhile, the B acid sites improved the selectivity of the direct desulfurization (DDS) reaction pathway. In addition, the B acid sites not only promoted the increase of DDS selectivity but also inhibited further deep hydrogenation of tetrahydrodibenzothiophene (THDBT) and hexahydrodibenzothiophene (HHDBT) in the hydrogenation (HYD) reaction pathway, thereby ensuring an increase in desulfurization efficiency while reducing hydrogen consumption. The fundamental reason was that the introduction of Y zeolite enhanced the acidity of the modified catalyst, especially the interaction between B acid sites and active metal promoted electron transfer, which adjusted the Fe species electronic defect structure, resulting in the improvement of HDS performance.
- Fe-based catalyst /
- Y zeolite /
- acidity /
- electronic defect structure /
- HDS /
- dibenzothiophene

HTML全文

图 1 载体和氧化态Fe基催化剂的XRD谱图

Figure 1 XRD patterns of supports and oxide Fe-based catalysts

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图 2 硫化态Fe基催化剂的XRD谱图

Figure 2 XRD patterns of sulfide Fe-based catalysts

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图 3 载体以及Fe基催化剂的（a）吸附-脱附等温曲线和（b）孔径分布

Figure 3 (a) N₂ physical adsorption-desorption isotherms and (b) pore size distribution of supports and oxide Fe-based catalysts

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图 4 载体和Fe基催化剂的SEM图

Figure 4 SEM images of supports and oxide Fe-based catalysts

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图 5 Fe基催化剂的EDS-Mapping图

Figure 5 EDS-Mapping images of oxide Fe-based catalysts

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图 6 Fe基催化剂的H₂-TPR谱图

Figure 6 H₂-TPR profiles of oxide Fe-based catalysts

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图 7 载体和Fe基催化剂的NH₃-TPD谱图

Figure 7 NH₃-TPD profiles of supports and oxide Fe-based catalysts

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图 8 载体和Fe基催化剂在（a）150 ℃（总酸）和（b）300 ℃（强酸）下的Py-IR谱图

Figure 8 Py-IR spectra of supports and oxide Fe-based catalysts with adsorbed pyridine at (a) 150 ℃ (total acid sites) and (b) 300 ℃ (strong acid sites)

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图 9 根据Fe 2p_3/2电子轨道的XPS得出该系列硫化态Fe基催化剂的硫化度

Figure 9 The SD of the Fe-based catalysts acquired from the XPS data of Fe 2p_3/2

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图 10 不同硫化态Fe基催化剂Fe 3p轨道的XPS谱图

Figure 10 XPS spectra of Fe 3p for sulfide Fe-based catalysts

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图 11 Fe基催化剂催化DBT的HDS性能

Figure 11 Sulfur removal rate of DBT over Fe-based catalysts

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图 12 （a）未改性Fe基催化剂和（b）改性后Fe基催化剂催化DBT的HDS反应路径

Figure 12 Reaction pathway of DBT over (a) unmodified Fe-based catalyst and (b) modified Fe-based catalyst

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图 13 Fe基催化剂的酸性位点和DDS选择性之间的关系

Figure 13 Relationship between the DDS selectivity and acid site for Fe-based catalysts

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表 1 载体以及Fe基催化剂的织构性质

Table 1 Textural properties of supports and Fe-based catalysts

Sample	Surface area (m²·g⁻¹)			Pore volume (cm³·g⁻¹)
Sample	BET^a	external	micropore^b	total^c	mesopore	micropore^b
USY	586	509	77	0.389	0.140	0.249
DY	578	533	45	0.364	0.103	0.261
GA	336	296	40	1.150	1.133	0.017
UGA	353	232	121	0.987	0.929	0.058
DGA	366	220	146	0.975	0.905	0.070
FZ@GA	225	200	25	0.737	0.727	0.010
FZ@UGA	270	159	111	0.724	0.671	0.053
FZ@DGA	248	154	94	0.714	0.669	0.045
^a–BET method; ^b–t-plot method; ^c–Volume adsorbed at p/p₀ =0.99.

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表 2 Fe基催化剂的H₂-TPR曲线对应的还原温度

Table 2 Reduction temperature corresponding to peak of oxide Fe-based catalysts from H₂-TPR

Sample	Temperature corresponding to reduction peak /℃
Sample	R1	R2	R3	R4
FZ@GA	307	390	463	540
FZ@UGA	279	365	443	585
FZ@DGA	271	371	448	542

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表 3 由Py-IR测得的改性前后载体和Fe基催化剂表面酸中心的类型和含量

Table 3 Concentrations of B acid sites (1545 cm⁻¹) and L acid sites (1455 cm⁻¹) acquired by Py-IR spectra

Sample	Weak acid sites /(μmol·g⁻¹)		Strong acid sites /(μmol·g⁻¹)		Total /(μmol·g⁻¹)
Sample	L	B	L	B	Total /(μmol·g⁻¹)
USY	189.9	105.3	133.0	101.0	529.1
DY	171.8	108.7	258.2	118.3	657.0
GA	198.0	0.0	77.6	0.0	275.7
UGA	150.7	24.9	67.2	46.4	289.2
DGA	148.7	33.9	115.1	98.0	395.7
FZ@GA	159.5	0.0	123.9	0.0	283.3
FZ@UGA	269.5	13.3	141.6	2.1	426.6
FZ@DGA	224.1	17.0	208.2	6.2	455.4
FZ@USY	203.9	90.4	164.0	45.2	503.5
FZ@DY	226.2	136.9	191.7	63.3	618.1

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表 4 硫化态Fe基催化剂中Fe物种的组成

Table 4 Composition of Fe species of sulfide Fe-based catalysts from XPS data

Sample	Concentration of Fe species /%					SD /%
Sample	FeS	Fe(III)-O	Fe(II)-O	FeZnS	FeS₂	SD /%
FZ@GA	17.7	17.3	22.3	19.6	23.0	60.4
FZ@UGA	23.7	7.8	22.4	28.7	17.4	69.8
FZ@DGA	22.4	6.0	24.0	29.6	18.0	70.0

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表 5 Fe基催化剂在催化DBT的HDS过程中的产物分布、反应选择性和反应速率常数

Table 5 Product distributions, pathway selectivity and k_HDS of HDS reaction for DBT over Fe-based catalysts

Sample	FeZn@GA	FeZn@UGA	FeZn@DGA
CPMCY	9.01	0	0
2-MCPB	3.19	0	0
Benzyl-CP	16.74	4.42	5.32
BCH	6.58	0.97	0.76
CHB	27.63	3.12	2.37
BP	22.20	62.96	68.21
THDBT + HHDBT	14.65	26.75	23.33
k_HDS ( × 10⁻⁴ mol/(g·h))	1.05	2.02	2.67
S_DDS	22.20	62.96	68.21
S_HYD	77.8	37.04	31.79
DDS/HYD	0.29	1.70	2.15
*–The data was determined with approximately 30% of the HDS rate via changing the WHSV at 360 ℃.

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