钨、钼、镍含量的改变对体相催化剂物化性质、加氢活性影响

王海涛; 徐学军; 王继锋; 刘东香; 冯小萍

钨、钼、镍含量的改变对体相催化剂物化性质、加氢活性影响

中国石油化工股份有限公司大连石油化工研究院, 辽宁大连 116045

基金项目:

中国石油化工集团公司项目 114083

详细信息

通讯作者:
WANG Hai-tao, Tel: 024-56389373，E-mail: wanghaitao.fshy@sinopec.com

中图分类号: TE624.93
计量
- 文章访问数: 116
- HTML全文浏览量: 65
- PDF下载量: 12
- 被引次数: 0
出版历程
- 收稿日期: 2017-05-10
- 修回日期: 2017-10-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-03-10

Effects of tungsten, molybdenum and nickel content chang on physicochemical properties and hydrogenation activity of bulk catalysts

Dalian Research Institute of Petrochemicals, SINOPEC, Dalian 116045, China

Funds:

The project was supported by China Petrochemical Corporation (Sinopec Group) 114083

摘要

摘要: 制备不同活性金属原子比的体相催化剂，通过BET、XRD、SEM、TEM、强度测定、堆积密度测定及小型活性评价手段，考察了活性金属钨、钼、镍含量的变化对体相催化剂物化性质和活性的影响。结果表明，保持W/Mo原子比不变，随着（W+Mo）/Ni的原子比减小，孔体积、比表面积、孔径增大，超深度加氢脱硫活性增强，在精制油硫含量小于10 μg/g，反应温度降低8 ℃。在（W+Mo）/Ni的原子比不变的条件下，W/Mo的原子比在0.28-1.85，随着原子比增大，孔体积、比表面积、超深度加氢脱硫活性没有明显变化。
- 体相催化剂 /
- 金属含量 /
- 原子比 /
- 加氢活性 /
- 物化性质
Abstract: Bulk catalysts with different active metal atomic ratios were prepared. The effects of changing active metal tungsten, molybdenum and nickel contents on the physicochemical properties and activity of bulk catalysts were investigated using various characterization instruments, such as BET, XRD, SEM, TEM, determination of strength, packing density and laboratory scale hydrogenation apparatus. The results show that pore volume, specific surface area, pore size and the activity of ultra-deep hydrodesulfurization were all increased with the decrease of (W+Mo)/Ni ratio, while W/Mo atomic ratio remained constant. The reaction temperature reduced by 8℃ when sulfur content of refined oil is less than 10 μg/g. And the pore volume, specific surface area, pore size and ultra-deep hydrodesulfurization activity did not change obviously with increase of the W/Mo atomic ratio in the range of 0.28-1.85 while the (W+Mo)/Ni atomic ratio was kept unchanged.
- bulk catalyst /
- physicochemical properties /
- metal content /
- hydrotreating activity /
- mole ratio

HTML全文

图 1 不同λ₁体相催化剂的孔径分布

Figure 1 BET pore size distribution curves of different (W+Mo)/Ni bulk catalysts

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图 2 不同λ₁体相催化剂的XRD谱图

Figure 2 XRD pattern of different (W+Mo)/Ni bulk catalysts

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图 3 不同λ₁体相催化剂的SEM照片

Figure 3 SEM images of different (W+Mo)/Ni bulk catalysts

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图 4 不同第ⅥB族金属与第Ⅷ族金属原子比的硫化态催化剂TEM照片

Figure 4 TEM images of different (W+Mo)/Ni sulfurized bulk catalysts

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图 5 不同λ₂体相催化剂的孔径分布

a: YP-λ₂-0.28；b: YP-λ₂-0.60；c: YP-λ₂-1.35；d: YP-λ₂-1.85；e: YP-λ₂-2.05

Figure 5 BET pore size distribution curves of different W/Mo bulk catalysts

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图 6 不同λ₂体相催化剂的XRD谱图

a: YP-λ₂-0.28；b: YP-λ₂-0.60；c: YP-λ₂-1.35；d: YP-λ₂-1.85

Figure 6 XRD patterns of different W/Mo bulk catalysts

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图 7 不同λ₂催化剂扫描电子显微镜(SEM)照片

Figure 7 SEM images of different W/Mo bulk catalysts

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图 8 不同λ₂硫化态催化剂透射电子显微镜(TEM)照片

Figure 8 TEM images of different W/Mo bulk catalysts

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表 1 不同第ⅥB族金属与第Ⅷ族金属原子比(λ₁ )体相催化剂的物化性质

Table 1 Physic-chemical properties of different (W+Mo)/Ni bulk catalysts

Catalyst	YP-λ₁-0.42	YP-λ₁-0.60	YP-λ₁-0.90	YP-λ₁-1.20	YP-λ₁-1.45	YP-λ₁-1.65	YP-λ₁-1.90
λ₁	0.42	0.60	0.90	1.20	1.45	1.65	1.90
NiO/%	38	30	24	18	15	12.3	9
v_P/(cm³·g^-1)	0.385	0.350	0.299	0.271	0.250	0.235	0.186
A_BET/(m²·g^-1)	223	208	195	184	168	151	125
d_P/nm	7.0	6.5	6.1	5.6	4.8	4.3	3.5
Stack density ρ/(g·cm^-3)	0.80	0.86	0.93	1.05	1.20	1.26	1.38
Crush strength/(N·mm^-1)	7.0	9.7	14.5	16.2	17.2	19.5	20.8

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表 2 不同λ₁催化剂WS₂/MoS₂片层平均长度和平均堆叠层数

Table 2 Average slab layers and slab length of different (W+Mo)/Ni sulfurized bulk catalysts

Catalyst	Slab layers N	Slab length L/nm
YP-λ₁-0.60	5.71	7.99
YP-λ₁-0.90	5.62	7.88
YP-λ₁-1.20	4.19	7.90
YP-λ₁-1.45	3.59	7.91

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表 3 不同λ₁体相催化剂镇海常三线柴油的对比

Table 3 Catalyst activity evaluation of different (W+Mo)/Ni bulk catalysts

Catalyst		YP-λ₁-0.90	YP-λ₁-1.20	YP-λ₁-1.45
Reaction temperature t/℃		base	base +5	base +8
Properties of feedstock and refined oil	material	refining oil	refining oil	refining oil
Density(20 ℃) ρ/(g·cm^-3)	0.859 6	0.830 3	0.829 6	0.830 0
Boiling range (ASTM-D86) t/℃(IBP-EBP)	202-373	181-373	156-373	166-373
w(S)/(μg·g^-1)	14 424	8.5	9.2	9.0
w(N)/(μg·g^-1)	389	1.0	1.0	1.0
w(aromatic hydrocarbons)/%	37	11.9	11.6	11.7
w(polycyclic aromatic hydrocarbons)/%	20.5	2.0	1.8	1.8
Cetane number	50.8	55.9	55.2	55.4

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表 4 不同λ₂体相催化剂的物化性质

Table 4 Physic-chemical properties of different W/Mo bulk catalyst

Catalyst	YP-λ₂-0.28	YP-λ₂-0.60	YP-λ₂-1.35	YP-λ₂-1.85	YP-λ₂-2.05
λ₂	0.28	0.60	1.35	1.85	2.05
v_P/(cm³·g^-1)	0.284	0.276	0.278	0.285	0.346
A_BET/(m²·g^-1)	182	175	181	185	218
d_P/nm	5.7	5.6	5.7	5.8	7.5
Stack density ρ/(g·cm^-3)	1.03	1.04	1.05	1.03	0.79
Crush strength/(N·mm^-1)	14.3	15.1	14.8	14.2	7.2

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表 5 不同λ₂硫化态催化剂WS₂/MoS₂片层平均长度和平均堆叠层数

Table 5 Average slab layer and slab length of different W/Mo sulfurized bulk catalysts

Catalyst	Slab layers N	Slab length L/nm
YP-λ₂-0.28	5.58	7.91
YP-λ₂-0.60	5.62	7.95
YP-λ₂-1.35	5.64	7.99
YP-λ₂-1.85	5.61	7.93

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表 6 不同λ₂体相催化剂的加氢活性评价

Table 6 Catalyst activity evaluation of different W/Mo bulk catalysts

Catalyst		YP-λ₂-0.28	YP-λ₂-0.60	YP-λ₂-1.35	YP-λ₂-1.85
Reaction temperature t/℃		base	base	base	base
Properties of feedstock and refined oil	material	refining oil	refining oil	refining oil	refining oil
Density(20 ℃) ρ/(g·cm^-3)	0.866 6	0.838 1	0.838 9	0.838 7	0.838 9
Boiling range (ASTM-D86) t/℃(IBP-EBP)	194-365	176-360	176-359	177-359	176-360
w(S)/(μg·g^-1)	13 000	7.7	7.5	7.8	8.0
w(N)/(μg·g^-1)	631	1.0	1.0	1.0	1.0
w(aromatic hydrocarbons)/%	25.2	16.6	16.5	16.7	16.4
w(polycyclic aromatic hydrocarbons)/%	13.6	3.1	3.1	3.0	3.0
Cetane number	44.5	51.4	51.2	51.3	51.2

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