无定形硅铝载体的酸性对费托蜡加氢裂化反应中柴油选择性的影响

李涛; 车晓莉; 云一峰; 陶智超; 赵春利; 杨勇; 李永旺

无定形硅铝载体的酸性对费托蜡加氢裂化反应中柴油选择性的影响

李涛^{1, 2, 3},
车晓莉⁴,
云一峰^{3, 5},
陶智超^{3, 5},
赵春利^{1, 2, 3},
杨勇^{1, 3, 5, ,},
李永旺^{1, 3, 5}

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
3.
煤炭间接液化国家工程实验室, 北京 101407
4.
山东公泉化工股份有限公司, 山东淄博 255400
5.
中科合成油技术有限公司, 北京 101407

基金项目:

中国科学院战略性先导专项 XDA07060200

详细信息

通讯作者:
杨勇, Tel: 010-69667699, E-mail: yyong@sxicc.ac.cn

中图分类号: O643
计量
- 文章访问数: 72
- HTML全文浏览量: 31
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2017-02-13
- 修回日期: 2017-03-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-05-10

Study of the relationship between the acidity of amorphous silica-alumina supports and diesel selectivity in Fischer-Tropsch wax hydrocracking

LI Tao^{1, 2, 3},
CHE Xiao-li⁴,
YUN Yi-feng^{3, 5},
TAO Zhi-chao^{3, 5},
ZHAO Chun-li^{1, 2, 3},
YANG Yong^{1, 3, 5
, ,},
LI Yong-wang^{1, 3, 5}

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
3.
National Engineering Laboratory for Indirect Coal Liquefaction, Beijing 101407, China
4.
Shangdong Gongquan Chemical CO. LTD., Zibo 255400, China
5.
Synfuels China Technology CO. LTD., Beijing 101407, China

Funds:

the Strategic Priority Research Program of the Chinese Academy of Sciences XDA07060200

摘要

摘要: 利用逐梯度铵交换处理的方法合成了三个织构性质相似、酸性不同的无定形硅铝载体，并通过XRD、N₂吸附-脱附、NH₃-TPD、Py-FTIR和NMR等手段对载体的物化性质进行了研究。经等体积浸渍负载贵金属Pt，制成加氢裂化催化剂，以费托蜡加氢裂化生产柴油为探针反应，研究了无定形硅铝载体的酸性与柴油选择性之间的构效关系。结果表明，柴油选择性主要与载体的B酸性质有关，受L酸的影响很小；催化剂载体的强B酸含量与柴油选择性成相反关系，载体强B酸的含量越低，柴油选择性越高；催化剂Pt/B-1具有相对最高的柴油选择性，在反应压力7.0 MPa，H₂/wax（volume ratio）=1 000：1，LHSV=1.0 h^-1，温度为370℃的条件下，C₂₂₊转化率为62.52%时，对柴油的选择性达87.12%，具有比文献报道及商业化无定形硅铝载体ASA制备的催化剂Pt/ASA相对更高的活性和柴油选择性。
- 加氢裂化 /
- 无定形硅铝 /
- 费托蜡 /
- 柴油 /
- 选择性
Abstract: Three amorphous silica-alumina supports with similar textural properties and different amounts of acidity were successfully synthesized through ammonium exchange processing and their structures, acidity properties and the coordination of Si and Al in the as-synthesized supports were characterized using XRD, N₂ adsorption-desorption, NH₃-TPD, Py-FTIR and NMR. Amorphous silica-alumina was impregnated into a solution of H₁₂N₄PtCl₂·XH₂O to obtain hydrocracking catalysts. The relationship between acidic properties of supports and catalytic performance was studied by hydrocracking of Fischer-Tropsch (F-T) wax to diesel in a continuous-flow type fixed-bed reactor as a model reaction. The results illustrated that the diesel selectivity was mainly related to Brønsted acid properties of the supports while Lewis acid showed little correlation. The amount of strong Brønsted acid was reversely related to the selectivity of diesel:the smaller the amount, the higher the selectivity. The as-synthesized Pt/B-1 catalyst showed high selectivity of 87.12% to diesel at the conversion of F-T wax of about 62.52%, under the reaction conditions of 370℃, 7.0 MPa, LHSV of 1.0 h^-1 and a hydrogen-to-wax ratio of 1 000:1. Pt/B-1 had better catalytic performance than Pt/ASA prepared by commercial amorphous silica-alumina (ASA).
- hydrocracking /
- amorphous silica-alumina /
- Fischer-Tropsch wax /
- diesel /
- selectivity

HTML全文

图 1 无定形硅铝载体的XRD谱图

Figure 1 XRD patterns of as-synthesized amorphous silica-alumina

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图 2 无定形硅铝载体的N₂吸附-脱附曲线和微孔孔径分布

Figure 2 N₂ adsorption-desorption isotherms and micropore size distributions of different amorphous silica-alumina supports

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图 3 无定形硅铝载体的NH₃-TPD谱图

Figure 3 Acidic properties of different amorphous silica-alumina supports upon NH₃-TPD

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图 4 无定形硅铝载体的²⁷Al MAS NMR谱图

Figure 4 ²⁷Al MAS NMR spectra of different amorphous silica-alumina supports

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图 5 无定形硅铝载体的²⁹Si MAS NMR谱图

Figure 5 ²⁹Si MAS NMR spectra of different amorphous silica-alumina supports

a: B-1; b: B-2; c: B-3

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图 6 费托蜡在无定形硅铝催化剂上的加氢裂化选择性

Figure 6 Selectivity to C_10-22 during hydrocracking of Fischer-Tropsch wax on as-synthesized catalysts

reaction conditions: 7.0 MPa, LHSV=1.0 h^-1, H₂/wax (volume ratio) = 1 000:1

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图 7 费托蜡在无定形硅铝催化剂上的加氢裂化转化率

Figure 7 Conversion of Fischer-Tropsch wax on as-synthesized hydrocracking catalysts

reaction conditions: 7.0 MPa, LHSV=1.0 h^-1, H₂/wax (volume ratio) = 1 000:1

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表 1 无定形硅铝载体样品的物化性质

Table 1 Physical and chemical properties of different amorphous silica-alumina samples

Sample	Content w/%^a		BET surface area A/(m²·g^-1) ^b			Pore volume v/(cm³·g^-1)	Average pore radius d/nm
Sample	Na₂O	Si/Al	micropore	external	total	Pore volume v/(cm³·g^-1)	Average pore radius d/nm
ASA	0.088	1.61	9	208	217	0.70	10.3
B-1	0.13	31.0	15	261	276	0.94	11.9
B-2	0.012	31.5	14	253	267	0.89	11.5
B-3	0.004 4	31.7	14	250	264	0.88	11.6
^a: obtained from final solid product by XRF; ^b: obtained by N₂-adsorption at-196 ℃ using micromeritic ASAP2020

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表 2 无定形硅铝载体的B酸及L酸含量

Table 2 Concentration of Brønsted and Lewis acid sites of different samples

Sample	Acidity /(μmol_Py·g^-1)
	Brønsted			Lewis
	200 ℃	350 ℃	200-350 ℃	200 ℃	350 ℃	200-350 ℃
ASA	12.28	1.20	11.08	95.97	38.33	57.64
B-1	26.84	1.26	25.58	32.90	22.51	10.39
B-2	28.60	6.23	22.37	42.99	37.18	5.81
B-3	20.85	4.02	16.83	45.59	35.52	10.07

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