小晶粒NiY分子筛的合成及其加氢裂化反应性能

孙劲晓; 王晓晗; 魏强; 周亚松

doi:10.1016/S1872-5813(24)60432-9

小晶粒NiY分子筛的合成及其加氢裂化反应性能

doi: 10.1016/S1872-5813(24)60432-9

中国石油大学(北京)重质油全国重点实验室, 北京 102249

基金项目: 国家自然科学基金 (22078360)资助

详细信息

通讯作者:
E-mail: qwei@cup.edu.cn

zhouyasong2011@163.com

中图分类号: O643
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出版历程
- 收稿日期: 2023-12-15
- 修回日期: 2024-01-27
- 录用日期: 2024-01-31
- 网络出版日期: 2024-03-09

Synthesis and hydrocracking performance of small crystal NiY zeolites

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

Funds: The project was supported by National Natural Science Foundation of China (22078360).

摘要

摘要: 通过原位合成法在小晶粒Y分子筛合成的过程中，引入Ni源合成了一系列不同Ni掺入量的小晶粒Y-xNi分子筛，将活性金属Ni预浸渍到Y分子筛的骨架中。将Y-xNi分子筛和ASA混合作为载体并采用等体积浸渍法负载Ni、W制备Cat-xNi系列加氢裂化催化剂。以正十六烷为反应物，探究其加氢裂化反应性能。采用扫描电子显微镜(SEM)、X-射线衍射(XRD)、N₂吸附-脱附、氨气程序升温脱附(NH₃-TPD)、氢气程序升温还原(H₂-TPR)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等表征手段分析了Ni的掺入对Y分子筛及催化剂理化性质的影响。结果表明，Ni主要取代Al引入Y分子筛骨架。在Y分子筛中适量掺入Ni会提高Y分子筛的相对结晶度以及Brønsted酸和Lewis酸位点的数量，但过量的Ni掺入不利于Y分子筛的结晶。Ni掺入削弱了金属与载体间的相互作用，提高了活性金属的硫化度及NiWS活性相的堆积数及分散度，调节了催化剂上金属中心与酸中心的匹配。催化性能评价表明，Ni改性有利于提高中间馏分产物(C₈−C₁₂)的选择性及收率。即同时增加Brønsted酸中心与NiWS活性中心数量、提高了金属中心与酸中心之间的协同作用，在提高转化率的同时避免过度裂化，提高中间馏分产物的收率。在360 ℃反应温度下，催化剂Cat-0.2Ni具有较高的n-C₁₆转化率和C₈−C₁₂产物收率，n-C₁₆转化率较Cat-0Ni提高了10.2个百分点，C₈−C₁₂产物收率为65.4%。采用原位合成法将活性金属Ni预浸渍在Y分子筛上可以有效调节裂化活性中心与加氢活性中心之间的平衡而提高催化活性和中间馏分产物的收率。
- Y分子筛 /
- 原位Ni修饰 /
- 催化剂 /
- 加氢裂化 /
- 中间馏分油
Abstract: A series of small crystal Y-xNi zeolites with different amounts of Ni doping were synthesized by an in situ synthesis method, in which Ni precursors were introduced during the synthesis of small crystal Y zeolites. The active metal Ni was pre-impregnated into the framework of the Y zeolite. Y-xNi series zeolite and ASA were mechanically mixed as support and loaded with Ni and W to prepare Cat-xNi series hydrocracking catalysts. The hydrocracking performance was investigated using n-hexadecane as the reactant. The effects of Ni doping on the physicochemical properties of Y zeolite and catalysts were analyzed by means of characterization such as scanning electron microscopy (SEM), X-ray diffraction (XRD), N₂-adsorption desorption, NH₃ temperature programmed desorption (NH₃-TPD), H₂ temperature programmed reduction (H₂-TPR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The results show that Ni mainly replaces Al into the framework of Y zeolite. The appropriate incorporation of Ni into Y zeolite increases the relative crystallinity of Y zeolite and the number of Brønsted and Lewis acid sites. However, excessive Ni incorporation is detrimental to the crystallization of Y zeolite and excessive non-framework Ni species will cover the surface Brønsted acid sites. Ni doping weakened the metal-support interactions, increased the sulfation of the active metal, the stacking number and dispersion of NiWS, and modified the matching between the metal and acid sites on the catalyst. The results of the catalyst evaluation showed that the introduction of Ni was favorable to improve the selectivity and yield of the middle distillate products (C₈−C₁₂). That is, increasing the number of Brønsted acid sites and NiWS active sites at the same time, improving the synergistic effect between the metal sites and the acid sites, improving the conversion while avoiding over-cracking, and increasing the yield of the middle distillate products. The catalyst Cat-0.2Ni had a higher n-C₁₆ conversion and C₈−C₁₂ product yield at the reaction temperature of 360 ℃, with the n-C₁₆ conversion increased by 10.2 percentage points compared with that of Cat-0Ni, and the C₈−C₁₂ product yield was 65.4%. Therefore, the pre-impregnation of active metal Ni on Y zeolite can effectively regulate the balance between the Hydrogenation and cracking performance to improve the catalytic activity and the yield of middle distillate products.
- Y zeolite /
- in-situ Ni modification /
- catalyst /
- hydrocracking /
- middle distillate

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图 1 Y-xNi系列分子筛的XRD谱图

Figure 1 XRD patterns of the synthesized Y-xNi zeolites (a) from 5° to 60° and (b) from 5.0° to 8.0°

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图 2 Y-xNi系列分子筛的SEM照片

Figure 2 SEM images of the synthesized Y-xNi zeolites

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图 3 Y-xNi系列分子筛的N₂吸附-脱附等温曲线（a）和孔径分布（b）

Figure 3 N₂ adsorption-desorption (a) and pore size distribution curves (b) of the synthesized Y-xNi zeolites

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图 4 Y-xNi系列分子筛的Ni 2p XPS（a）, O 1s XPS（b）, Al 2p XPS（c）和Si 2p XPS（d）谱图及其分峰结果

Figure 4 Decomposition results of Ni 2p XPS(a), O 1s XPS(b), Al 2p XPS(c) and Si 2p XPS(d) spectra for the synthesized Y-xNi zeolites

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图 5 Y-xNi系列分子筛的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of the synthesized Y-xNi zeolites

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图 6 Y-xNi系列分子筛的Py-FTIR谱图

Figure 6 Py-FTIR spectra of the synthesized Y-xNi zeolites

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图 7 Cat-xNi系列催化剂未硫化NiW催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles for the non-sulfided NiW catalysts

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图 8 Cat-xNi系列硫化态NiW催化剂的HRTEM照片

Figure 8 HRTEM images of the sulfided NiW catalysts

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图 9 硫化NiW催化剂上WS₂片晶的长度（a）和堆叠层数（b）的分布

Figure 9 Distributions of layer length (a) and stacking number (b) of WS₂ slabs on the sulfided NiW catalysts

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图 10 硫化NiW系列催化剂的W 4f XPS（a）和Ni 2p XPS（b）谱图及其分峰结果

Figure 10 Decomposition results of W 4f XPS(a) and Ni 2p XPS(b) spectra for the sulfided NiW series catalysts

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图 11 Cat-xNi系列硫化催化剂在不同反应温度下n-C₁₆的转化率（a）、C₈−C₁₂的选择性（b）和收率（c）以及在360 ℃条件下重复三次实验后不同催化剂的C₈−C₁₂的收率（d）

Figure 11 Conversion of n-C₁₆ (a), selectivity of C₈−C₁₂ (b) and yield of C₈−C₁₂ (c) over the sulfided NiW catalysts at different reaction temperatures and yield of C₈−C₁₂ after three repetitive experiments at 360 ℃ for different sulfided Cat-xNi catalysts (d)

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表 1 不同Ni含量杂原子Y-xNi分子筛的理化性质

Table 1 physicochemical of the synthesized Y-xNi zeolites with different Ni content

Sample	n(NiO/Al₂O₃)		Relative crystallinity^b/ %	Crystal cize^c/ nm	S_BET/ (m²·g⁻¹)	v_total/ (cm³·g⁻¹)	Average pore diameter/ nm
Sample	theoretical	actual^a	Relative crystallinity^b/ %	Crystal cize^c/ nm	S_BET/ (m²·g⁻¹)	v_total/ (cm³·g⁻¹)	Average pore diameter/ nm
Y-0Ni	0	0	100	125	634.4	0.64	6.7
Y-0.1Ni	0.1	0.09	102	136	612.1	0.62	6.4
Y-0.2Ni	0.2	0.17	97	141	600.6	0.61	6.1
Y-0.3Ni	0.3	0.26	92	146	588.4	0.59	5.9
Y-0.4Ni	0.4	0.37	88	152	560.2	0.55	5.1
^a: Calculated from XRF results (test sample was HY-xNi zeolites after ion-exchange); ^b: Calculated from XRD results and Eq. (1); ^c: Statistically calculated from SEM image results.

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表 2 Y-xNi系列分子筛上各物种分峰拟合

Table 2 XPS deconvolution results of the synthesized Y-xNi zeolites

Catalyst	Si−O−Si/%	Si−O−H/%	Si−O−Al/%	Ni−O/%	Ni²⁺/%	Ni³⁺/%
Y-0Ni	39.6	28.1	32.3	−	−	−
Y-0.1Ni	37.3	25.8	23.5	13.4	43.0	57.0
Y-0.2Ni	38.1	29.1	17.6	15.2	46.7	53.3
Y-0.3Ni	38.8	30.0	13.4	17.8	50.1	49.9
Y-0.4Ni	39.1	30.8	10.9	19.2	55.4	44.6

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表 3 Y-xNi系列分子筛的酸类型及酸量

Table 3 Acidity of the synthesized Y-xNi zeolites

Sample	Acidity/(μmol·g⁻¹)
	total acid sites (200 ℃)				medium and strong acid sites (350 ℃)				total^d
	L	B	L+B	B/L	L	B	L+B	B/L	total^d
Y-0Ni	96	220	316	2.3	45	158	206	3.5	414
Y-0.1Ni	125	233	358	1.9	63	164	227	2.6	452
Y-0.2Ni	162	242	404	1.5	88	171	259	1.9	486
Y-0.3Ni	193	254	447	1.3	107	182	289	1.7	522
Y-0.4Ni	228	257	485	1.1	124	189	313	1.5	591
^d: Calculated from NH₃-TPD results.

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表 4 硫化催化剂上WS₂的平均长度、堆垛层数、f_w值

Table 4 Average length, stacking number, f_w values of WS₂ slabs of the sulfided catalysts

Catalyst	Length/nm	Stacking number	f_w
Cat-0Ni	3.65	3.54	0.34
Cat-0.1Ni	3.61	3.55	0.35
Cat-0.2Ni	3.56	3.58	0.36
Cat-0.3Ni	3.48	3.58	0.37
Cat-0.4Ni	3.65	3.47	0.32

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表 5 硫化NiW系列催化剂上各物种分峰拟合结果

Table 5 XPS deconvolution results of the sulfide NiW series catalysts

Catalyst	WS₂/%	WO_xS_y/%	WO₃/%	Ni_sulfidation/%	NiWS/%	Ni_xS_y/%	NiO/%
Cat-0Ni	68.1	10.2	21.7	70.1	58.6	11.5	32.9
Cat-0.1Ni	68.7	11.4	19.9	68.3	59.1	9.2	31.7
Cat-0.2Ni	69.0	11.8	19.2	69.5	59.7	9.8	30.5
Cat-0.3Ni	69.2	12.1	18.7	70.2	60.8	9.4	29.8
Cat-0.4Ni	51.8	9.8	38.4	63.6	52.9	10.7	36.4

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表 6 360 ℃下五种催化剂的n-C₁₆加氢裂化活性数据

Table 6 Hydrocracking results of n-C₁₆ on five catalysts at 360 ℃

Catalyst	k^a/(mol·g^–1·h⁻¹)	TOF^a,b/h⁻¹	n-C₁₆ conversion/%	C₈−C₁₂ selectivity/%	C₈−C₁₂ yield/%
Cat-0Ni	1.09×10⁻²	25.79	65.2	88.9	58.1
Cat-0.1Ni	1.22×10⁻²	27.32	71.3	86.6	61.7
Cat-0.2Ni	1.31×10⁻²	28.05	75.1	86.0	64.6
Cat-0.3Ni	1.44×10⁻²	29.44	76.2	75.4	57.5
Cat-0.4Ni	1.68×10⁻²	38.19	81.0	68.9	55.8
^a: Changing the LHSV for n-C₁₆ conversion of about 30%, ^b: The number of n-C₁₆ molecules converted per hour per mole of W atoms.

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