NiMo/Al<sub>2</sub>O<sub>3</sub>-USY催化剂上中低温煤焦油加氢裂化性能研究

杨加可; 左童久; 鲁玉莹; 曾武松; 陆江银

NiMo/Al₂O₃-USY催化剂上中低温煤焦油加氢裂化性能研究

新疆大学化学化工学院石油天然气精细化工教育部重点实验室, 新疆乌鲁木齐 830046

基金项目:

国家自然科学基金 21366030

详细信息

中图分类号: TQ032
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出版历程
- 收稿日期: 2019-05-28
- 修回日期: 2019-07-04
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-09-10

Catalytic performance of NiMo/Al₂O₃-USY in the hydrocracking of low-temperature coal tar

Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education, Xinjiang University, Urumqi 830046, China

Funds:

the National Natural Science Foundation of China 21366030

More Information

Corresponding author: LU Jiang-yin, E-mail: jiangyinlu6410@163.com

摘要

摘要: 采用等体积浸渍法制得一系列NiMo/Al₂O₃-USY催化剂，在200 mL固定床上考察了不同金属负载量对其中低煤焦油加氢裂化催化性能的影响，进一步用NH₄F溶液改性USY以提高催化剂的脱硫性能，并结合XRD、氮气吸附-脱附、XPS、HR-TEM、H₂-TPR和NH₃-TPD等手段对催化剂进行了表征分析。结果表明，NiMo/Al₂O₃-USY催化剂适宜的MoO₃负载量为15%（质量分数）；当MoO₃含量超过15%后，MoS₂活性相在载体上团聚，硫化程度趋于稳定，强酸酸量和孔径减少，增加金属负载量对煤焦油加氢裂化转化率影响较小。NH₄F改性USY可增大NiMo/Al₂O₃-USY催化剂的孔径，有利于提高煤焦油加氢裂化转化率。表面强酸酸量减少后，产品中的硫含量明显增加，说明强酸酸量是影响产物硫含量的关键因素。当NH₄F浓度为0.6 mol/L时，NH₄F改性USY制得的NM0.6催化剂上煤焦油加氢裂化的转化率为87.65%，产品汽油馏分（≤ 180 ℃）硫含量为5.96 mg/kg，柴油馏分（180-320 ℃）硫含量为34.98 mg/kg。
- 中低温煤焦油 /
- 加氢裂化 /
- 改性USY /
- 硫含量 /
- NiMo/Al₂O₃-USY
Abstract: A series of NiMo/Al₂O₃-USY catalysts with different MoO₃ contents were prepared through incipient wetness method and further modified with NH₄F. The NiMo/Al₂O₃-USY catalysts were characterized by XRD, XPS, HR-TEM, NH₃-TPD, H₂-TPR and N₂ adsorption and their catalytic performance in the hydrocracking of low-temperature coal tar (LTCT) was investigated in a 200 mL fixed-bed reactor. The results indicate that the appropriate MoO₃ content is 15% (mass ratio); higher MoO₃ content may lead to the agglomeration of active metals on the support, although it has little influence on the sulfidation degree of Mo species and the conversion of coal tar upon hydrocracking. In addition, the amount of strong acid sites and pore diameter decrease gradually with a further increase in the MoO₃ content, which is disadvantageous for deep hydrocracking. The modification of USY zeolite with NH₄F solution can enlarge the average pore diameter of resultant NiMo/Al₂O₃-USY catalysts and then improve the residue conversion of coal tar. However, the amount of strong acid sites decreases obviously when the concentration of NH₄F solution exceeds 0.6 mol/L, which may lead to an increase of the sulfur content in the hydrocracking product. Over the NiMo/Al₂O₃-USY catalyst modified with 0.6 mol/L NH₄F solution, the residue conversion of coal tar reaches 87.65%; the sulfur contents in the gasoline fraction (< 180 ℃) and diesel fraction (180-320 ℃) are 5.96 and 34.98 mg/kg, respectively.
- low-temperature coal tar /
- hydrocracking /
- modified USY /
- sulfur content /
- NiMo/Al₂O₃-USY

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图 1 浸渍制备催化剂流程示意图

Figure 1 Process of catalysts production

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图 2 Process of catalysts production

Figure 2 Simplified schematic diagram of hydrocracking process

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图 3 不同金属含量催化剂的XRD谱图

Figure 3 XRD patterns of various NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

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图 4 不同金属含量催化剂的N₂吸附-脱附曲线(a)和相应孔径分布(b)

Figure 4 Nitrogen adsorption and desorption isotherms (a) and pore size distribution curves (b) of various NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

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图 5 不同金属含量催化剂的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of various NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

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图 6 还原后的不同金属含量催化剂的Mo 3d谱图

Figure 6 XPS spectra of various NiMo/USY-Al₂O₃ catalysts after sulfidation

(a): NiMo-9; (b): NiMo-12; (c): NiMo-15; (d): NiMo-18; (e): NiMo-21

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图 7 不同金属含量催化剂的HR-TEM照片

Figure 7 HR-TEM analysis of various NiMo/USY-Al₂O₃ catalysts after sulfidation

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图 8 催化剂的MoS₂片层长度和层数的分布图

Figure 8 MoS₂ length (a) and stack layer (b) distribution of various NiMo/USY-Al₂O₃ catalysts after sulfidation

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图 9 不同金属含量催化剂的煤焦油加氢产物分布

Figure 9 Performances of NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents in LTCT hydrocracking

(a): product distribution and residue conversion (Rc); (b): Gaseous product distribution reaction condition: t=395℃, p=8MPa, WHSV = 0.6h^-1, H₂/oil = 800

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图 10 不同金属负载量催化剂煤焦油加氢后产物的硫含量

Figure 10 Sulfur contents in the products for LTCT hydrocracking over NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

reaction condition: t=395℃, p=8MPa, WHSV=0.6h^-1, H₂/oil=800

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图 11 不同NMy催化剂的N₂吸附-脱附曲线(a)和相应孔径分布(b)

Figure 11 Nitrogen adsorption and desorption isotherms of NMy catalysts (a) and their pore size distribution (b)

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图 12 不同NMy催化剂的XRD谱图

Figure 12 XRD patterns of the NMy catalysts

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图 13 不同NMy催化剂的NH₃-TPD谱图

Figure 13 NH₃-TPD profiles of the NMy catalysts

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图 14 不同NMy催化剂的H₂-TPR谱图

Figure 14 H₂-TPR profiles of the NMy catalysts

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图 15 不同NMy催化剂的煤焦油加氢性能对比

Figure 15 Product distribution and residue conversion (Rc) (a) and sulfur content (b) for LTCT hydrocracking over various NMy catalysts

reaction conditiona: t=395℃, p=8MPa, WHSV = 0.6h^-1, H₂/oil = 800

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表 1 原材料的基本性质

Table 1 Properties of the LTCT feedstock

Item	Value
Density ρ/(g·cm^-³)	0.9548
Elemental analysis w/%
C	84.97
H	11.53
S	0.15
Distillation range t/℃
IBP/10%	199/265
30%/50%	293/351
90%/FBP	467/504

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表 2 不同金属含量催化剂的织构参数

Table 2 Textural properties of NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

Catalyst	A_BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)			Pore diameter d/nm
Catalyst	A_BET /(m²·g^-1)	v_total	v_micro	v_macro	Pore diameter d/nm
CAY	359	0.30	0.007	0.297	4.41
NiMo-9	346	0.32	0.021	0.307	3.80
NiMo-12	280	0.20	0.005	0.195	4.30
NiMo-15	257	0.19	0.005	0.188	4.25
NiMo-18	230	0.21	0.009	0.205	3.98
NiMo-21	191	0.18	0.006	0.1756	3.98

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表 3 不同金属含量催化剂的酸性分布

Table 3 Acid site distribution of NiMo/USY-Al₂O₃ catalysts with different MoO₃ contents

Catalyst	20-200℃		200-350℃		350-600℃		Overall relative value
Catalyst	area (a.u.)	relative	area (a.u.)	relative	area (a.u.)	relative	Overall relative value
CAY70	26.71	1	44.32	1	28.97	1	1
NiMo-9	31.06	1.43	46.79	1.3	22.15	0.94	1.23
NiMo-12	28.85	1.49	45.82	1.42	25.32	1.2	1.38
NiMo-15	27.89	1.35	45.63	1.33	26.48	1.18	1.3
NiMo-18	30.75	1.38	48.49	1.28	20.76	0.84	1.17
NiMo-21	29.52	1.38	53.74	1.52	16.74	0.72	1.25

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表 4 不同金属含量催化剂硫化后的价态分布

Table 4 Valence distribution of various NiMo/USY-Al₂O₃ catalysts after sulfidation

Catalyst	Ratio of different Mo species /%
Catalyst	Mo⁴⁺	Mo⁵⁺	Mo⁶⁺	total
NiMo-9	57	19	24	100.00
NiMo-12	65	17	18	100.00
NiMo-15	78	15	7	100.00
NiMo-18	82	14	5	100.00
NiMo-21	86	11	3	100.00

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表 5 不同金属含量催化剂的平均MoS₂片层长度和层数

Table 5 Average length and stack layer number of various NiMo/USY-Al₂O₃ catalysts after sulfidation

Catalyst	Average length of slabs d/nm	Average stack layer number of slabs
NiMo-9	3.63	3.56
NiMo-12	3.06	2.2
NiMo-15	3.88	3.01
NiMo-18	3.59	2.63
NiMo-21	3.94	2.92

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表 6 不同NMy催化剂的织构参数

Table 6 Textural properties of the NMy catalysts

Catalyst	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)			Average pore diameter d/nm
Catalyst	Surface area A/(m²·g^-1)	v_total	v_micro	v_macro	Average pore diameter d/nm
NiMo-15	257	0.19	0.005	0.188	4.14
NiMo-15(0.3)	254	0.22	0.008	0.212	3.93
NiMo-15(0.6)	248	0.22	0.006	0.216	4.36
NiMo-15(0.9)	254	0.24	0.007	0.238	4.38
NiMo-15(1.2)	268	0.22	0.004	0.2189	4.45
NiMo-15(1.5)	253	0.25	0.010	0.239	4.40

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表 7 不同NMy催化剂的酸性分布

Table 7 Acid sites distribution of the NMy catalysts

Catalyst	20-200℃		200-350℃		350-600℃		Overall relative value
Catalyst	area (a.u.)	relative	area (a.u.)	relative	area (a.u.)	relative	Overall relative value
NiMo-15	926.7	1	1039	1	582.4	1	1
NM0.3	1001	1.08	933	0.9	388	0.67	0.91
NM0.6	930.5	1	1071	1.03	305.8	0.53	0.91
NM0.9	840	0.91	1108	1.07	248	0.43	0.86
NM1.2	746.6	0.81	1068	1.03	218.6	0.38	0.8
NM1.5	682.9	0.74	820.2	0.79	99.4	0.17	0.63

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