多级孔Hβ沸石对NiWP/Hβ-Al<sub>2</sub>O<sub>3</sub>催化剂柴油加氢性能的影响

王海彦; 宋盼盼; 王钰佳

多级孔Hβ沸石对NiWP/Hβ-Al₂O₃催化剂柴油加氢性能的影响

王海彦^{1, 2, ,},
宋盼盼¹,
王钰佳¹

1.
辽宁石油化工大学, 辽宁抚顺 113001
2.
中国石油大学(华东), 山东青岛 266555

基金项目:

辽宁省教育厅 L2014152

详细信息

中图分类号: TQ426.95
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- 被引次数: 0
出版历程
- 收稿日期: 2015-11-09
- 修回日期: 2016-01-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-04-30

Influence of hierarchically mesoporous Hβ zeolite on the performance of NiWP/Hβ-Al₂O₃ catalysts in diesel oil hydro-upgrading

1.
Liaoning Shihua University, Fushun 113001, China
2.
China University of Petroleum (East China), Qingdao 266555, China

More Information

Corresponding author: Tel： 13941336296， E-mail： fswhy@126.com.

摘要

摘要: 采用碱处理法制备多级孔Hβ沸石,以不同比例与Al₂O₃混合,得到由Hβ沸石与Al₂O₃组成的混合载体,再采用等体积浸渍法制备了NiWP/Hβ-Al₂O₃系列催化剂。通过XRD、BET和NH₃-TPD等手段对载体及催化剂进行了表征,以催化裂化柴油(FCC)为原料,在小型固定床反应器上,研究了多级孔Hβ沸石对NiWP/Hβ-Al₂O₃催化剂加氢反应性能的影响。结果表明,载体中加入质量分数为15%Hβ沸石,NiWP/Hβ-Al₂O₃催化剂柴油加氢性能最好;在该催化剂上,360 ℃、8.0 MPa、体积空速为1.0 h^-1和氢油体积比800的操作条件下,脱硫率达到99.77%,催化裂化柴油的密度由0.927 g/cm³下降到0.837 g/cm³,十六烷值由13.78提高到55.39。
- 碱处理 /
- Hβ沸石 /
- 催化裂化柴油 /
- 加氢脱芳 /
- 加氢脱硫
Abstract: Hβ-Al₂O₃ composite supports were prepared through mechanically mixing Al₂O₃ with hierarchically mesoporous Hβ zeolite obtained by desilication with NaOH solution; bifunctional NiWP/Hβ-Al₂O₃ catalysts were then obtained by impregnation method. The composite supports and NiWP/Hβ-Al₂O₃ catalysts were characterized by XRD, BET and NH₃-TPD; the effect of Hβ addition on the catalytic performance of NiWP/Hβ-Al₂O₃ in diesel oil hydro-upgrading was investigated in a fixed bed reactor with fluid catalytic cracking (FCC) diesel as the feed. The results showed that by adding 15% Hβ in the Hβ-Al₂O₃ composite support, NiWP/Hβ-Al₂O₃ catalyst performs best in diesel oil hydro-upgrading; under 360 ℃, 8 MPa, volume space velocity of 1.0 h^-1 and volumetric hydrogen/oil ratio of 800, the desulfurization degree reaches 99.77%, the density of FCC diesel oil is decreased from 0.927 to 0.837 g/cm³, while the cetane value is increased from 13.78 to 55.39.
- alkali treatment /
- Hβ zeolite /
- FCC diesel oil /
- hydro-dearomatization /
- hydrodesulfurization

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图 1 Hβ(p)和Hβ(m)的XRD谱图

Figure 1 XRD patterns of parent Hβ(p) and modified Hβ(m)

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图 2 Hβ(p)和Hβ(m)沸石N₂吸附-脱附等温曲线

Figure 2 N₂ adsorption-desorption isotherms of parent Hβ(p) and modified Hβ(m) zeolites

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图 3 Hβ(p)和Hβ(m)分子筛的NH₃-TPD谱图

Figure 3 NH₃-TPD profiles of parent Hβ(p) and modified Hβ(m) zeolites

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图 4 NiWP/Hβ-Al₂O₃催化剂的XRD谱图

Figure 4 XRD patterns of NiWP/Hβ-Al₂O₃ catalysts with different contents of Hβ in the composite Hβ-Al₂O₃ supports

a: NiWP/Al₂O₃; b: NiWP/S(10); c: NiWP/S(15); d: NiWP/S(20); e: NiWP/S(30)

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图 5 NiWP/Hβ-Al₂O₃催化剂的孔径分布

Figure 5 Pore size distribution curves of of NiWP/Hβ-Al₂O₃ catalysts with different contents of Hβ in the composite Hβ-Al₂O₃ supports

a: NiWP/Al₂O₃; b: NiWP/S(10); c: NiWP/S(15); d: NiWP/S(20); e: NiWP/S(30); f: Hβ(m)

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图 6 Hβ(m)沸石及不同催化剂的吡啶吸附Py-FTIR谱图

Figure 6 Pyridine-IR spectra of various catalysts and Hβ(m)

a: NiWP/Al₂O₃; b: NiWP/S(10); c: NiWP/S(15); d: NiWP/S(20); e: NiWP/S(30); f: Hβ(m)

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图 7 Hβ(m)、Al₂O₃和S(15)的SEM 照片

Figure 7 SEM images of Hβ(m),Al₂O₃ and S(15)

(a): Hβ(m); (b): Al₂O₃; (c): S(15)

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图 8 不同催化剂的加氢脱硫率

Figure 8 Hydrodesulphurization ratio of diesel oil over various catalysts

■: NiWP/Al₂O₃; ●: NiWP/S(10); ▲: NiWP/S(15); ▼: NiWP/S(20); ◄: NiWP/S(30)

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图 9 不同催化剂上改质柴油的十六烷值

Figure 9 Cetane number (CN) of the upgraded diesel oil obtained over various catalysts

■: NiWP/Al₂O₃; ●: NiWP/S(10); ▲: NiWP/S(15); ▼: NiWP/S(20); ◄: NiWP/S(30)

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表 1 Hβ(m)沸石及不同催化剂孔结构性质

Table 1 Texture properties of various catalysts and Hβ(m)

Sample	A_BET/(m²·g^-1)	v_total/(mL·g^-1)	d_aver/nm
NiWP/Al₂O₃	234	0.56	8.78
NiWP/S(10)	260	0.54	8.09
NiWP/S(15)	274	0.53	7.66
NiWP/S(20)	282	0.54	7.12
NiWP/S(30)	306	0.52	7.02
Hβ(m)	381	0.48	5.07

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表 2 Hβ(m)沸石及不同载体的酸量

Table 2 Acid amounts of various supports and Hβ(m)

Acid strength	Amounts of acid sites /(μmol·g^-1)
Acid strength	Al₂O₃	S(10)	S(15)	S(20)	S(30)	Hβ(m)
Weak	65.11	118.94	146.82	174.75	230.24	583.63
Moderate	55.15	49.50	46.67	43.85	38.54	-
Strong	13.78	34.36	44.68	54.91	75.57	224.52
Total acid	134.04	202.80	238.27	273.51	344.35	805.15

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表 3 不同催化剂的酸量

Table 3 Acid amounts of various catalysts

Acid strength	Amounts of acid sites /(μmol·g^-1)
Acid strength	NiWP/Al₂O₃	NiWP/S(10)	NiWP/S(15)	NiWP/S(20)	NiWP/S(30)
Weak	79.24	113.62	141.69	168.11	186.88
Moderate	33.72	41.69	41.36	38.37	35.55
Strong	2.16	32.56	40.53	62.79	68.11
Total acid	115.12	187.87	223.59	269.27	290.53

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表 4 FCC柴油和NiWP/Al₂O₃、NiWP/S(15)催化剂上加氢产品的性质

Table 4 Properties of FCC diesel oil and hydrogenated products over the NiWP/Al₂O₃ and NiWP/S(15) catalysts

Properties	FCC	NiWP/Al₂O₃	NiWP/S(15)
Density /(g·mL^-1)	0.927	0.860	0.837
w(S) /(μg·g^-1)	3990	10	8.8
w(N) /(μg·g^-1)	721	33	41
Boiling range t/℃
IBP	171	162	104
50%	286	265	261
FBP	352	344	330
Diesel yield	-	98.7	95.3
(>165 ℃) w/%
C/H (mol ratio)	7.86	5.80	6.58
Hydrocarbon
component w/%
Chain alkanes	27.3	29.91	34.35
Cyclanic	12.2	16.66	20.29
Total aromatics	60.5	53.43	45.56
Monocyclic aromatic	27.3	48.02	45.41
Polycyclic aromatic	33.2	5.41	0.15
hydrocarbons

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