Co/Al2O3-SiO2催化剂的F-T反应性能的研究

郭舒鹏; 王民; 王俊刚; 马中义; 贾丽涛; 侯博; 李德宝

Co/Al₂O₃-SiO₂催化剂的F-T反应性能的研究

郭舒鹏^{1, 2},
王民^{1, 2},
王俊刚¹,
马中义^1, ,,
贾丽涛¹,
侯博¹,
李德宝^1, ,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目:

山西省基础研究基金 201601D021044

山西省基础研究基金 201701D121037

详细信息

中图分类号: O643
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- 文章访问数: 74
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- 被引次数: 0
出版历程
- 收稿日期: 2017-09-05
- 修回日期: 2017-12-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Study on the F-T reaction performance of Co/Al₂O₃-SiO₂ catalyst

GUO Shu-peng^{1, 2},
WANG Min^{1, 2},
WANG Jun-gang¹,
MA Zhong-yi^{1
, ,},
JIA Li-tao¹,
HOU Bo¹,
LI De-bao^{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:

Shanxi Basic Research Fund 201601D021044

Shanxi Basic Research Fund 201701D121037

More Information

Corresponding author: MA Zhong-yi, E-mail:mazhgyi@sxicc.ac.cn; LI De-bao, E-mail:dbli@sxicc.ac.cn

摘要

摘要: 通过浸渍法制备不同含量SiO₂改性的Co/Al₂O₃催化剂, 结合N₂吸附-脱附、XRD、H₂-TPR、XPS等表征手段, 研究SiO₂助剂对钴基催化剂物相结构、还原行为及F-T合成性能的影响。结果表明, 适量的SiO₂改性后, 有效地减弱了载体与活性组分钴之间的相互作用, 显著地提高了催化剂的还原度和催化活性。但继续增加SiO₂的含量, 催化剂的还原度继续提高, 分散度同时下降32%, 与未改性之前相比, 催化剂的活性基本没有改变。
- 费托合成 /
- 二氧化硅改性 /
- 还原度
Abstract: The γ-Al₂O₃ modified with different content of SiO₂ by impregnation method was used as supports to prepare Co/Al₂O₃ catalyst.The effects of SiO₂ additives on phase structure of the cobalt-based catalysts, reduction behavior and the influence on the F-T synthesis performance were studied by using N₂ adsorption, XRD, H₂-TPR and XPS characterization methods and activity test.The results showed that with the introduction of SiO₂, the interaction between support and cobalt was effectively weakened, thus the reducibility and catalytic activity of the catalysts were significantly improved.However, when the amount of SiO₂ continued to increase, the reduction degree of the catalyst continued to improve, but the dispersion decreased by 32% at the same time.Compared with unmodified Co/Al₂O₃ catalyst, the activity of the catalyst remained basically unchanged.
- Fischer-Tropsch synthesis /
- SiO₂ modification /
- reducibility

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图 1 催化剂的XRD谱图

a:Co/Al₂O₃-20SiO₂; b:Co/Al₂O₃-10SiO₂;
c:Co/Al₂O₃-5SiO₂; d:Co/Al₂O₃

Figure 1 XRD patterns of the catalysts

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图 2 催化剂和载体的TEM照片

(a):Co/Al₂O₃; (b):Co/Al₂O₃-20SiO₂

Figure 2 TEM images of the catalysts

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图 3 催化剂的H₂-TPR谱图

a:Co/Al₂O₃-20SiO₂; b:Co/Al₂O₃-10SiO₂;
c:Co/Al₂O₃-5SiO₂; d:Co/Al₂O₃

Figure 3 H₂-TPR profiles of the catalysts

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图 4 催化剂的Co 2p XPS谱图

a:Co/Al₂O₃-20SiO₂; b:Co/Al₂O₃-10SiO₂;
c:Co/Al₂O₃-5SiO₂; d:Co/Al₂O₃

Figure 4 XPS spectra of Co 2p of the catalysts

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表 1 载体和催化剂的物理化学性质

Table 1 Physico-chemical properties of the supports and the catalysts

Sample	A_BET/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm	Co crystalline ^a d/nm	H₂-TPD^b dispersion/%	H₂-TPR^c reducibility/%
Al₂O₃	188	0.52	8.3	-	-	-
Al₂O₃-5SiO₂	181	0.49	8.3	-	-	-
Al₂O₃-10SiO₂	178	0.47	8.2	-	-	-
Al₂O₃-20SiO₂	163	0.42	8.0	-	-	-
Co/Al₂O₃	139	0.34	8.0	7.1	4.99	28.4
Co/Al₂O₃-5SiO₂	138	0.33	7.9	7.7	4.94	38.2
Co/Al₂O₃-10SiO₂	132	0.30	7.8	8.9	4.88	53.5
Co/Al₂O₃-20SiO₂	115	0.27	7.6	10.4	3.36	63.4
^a d(Co) =0.75 d(Co₃O₄); the average particle size of Co₃O₄ calculated from XRD diffraction peak at 36.8°; ^b calculated from H₂ chemisorption; ^c calculated by H₂-TPR from 373 to 673 K

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表 2 催化剂的表面组成

Table 2 Surface composition of the catalysts

Sample	Co 2p_3/2 E_B/eV		I_CSS/I_Co₃O₄	Surface atom ratio^b
Sample	Co₃O₄	CSS^a	I_CSS/I_Co₃O₄	I_Si/I_Al
Co/Al₂O₃	779.275	782.566	0.785	-
Co/Al₂O₃-5SiO₂	779.782	782.051	0.640	0.120
Co/Al₂O₃-10SiO₂	779.795	782.076	0.599	0.224
Co/Al₂O₃-20SiO₂	779.834	782.058	0.737	0.319
^a:cobalt surface species; ^b:obtained by XPS measurement

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表 3 催化剂的反应性能

Table 3 Catalytic performance of the catalysts for F-T

Catalyst	Temperature t/℃	CO conversion x/%	Hydrocarbon selectivity s/%
Catalyst	Temperature t/℃	CO conversion x/%	CH₄	C_2-4	C₅₊
Co/Al₂O₃	210	23.77	14.99	5.54	79.47
	220	45.60	14.00	6.60	79.40
Co/Al₂O₃-5SiO₂	210	24.63	10.33	4.53	85.13
	220	48.01	12.88	6.75	80.37
Co/Al₂O₃-10SiO₂	210	38.12	10.66	5.44	83.89
	220	62.05	11.49	8.73	79.79
Co/Al₂O₃-20SiO₂	210	21.03	11.49	5.84	82.67
	220	44.08	14.71	8.21	77.08
reaction conditions:2 MPa, GHSV=1000 h^-1, H₂/CO(volume ratio)=2

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