载体酸性对Pt/USY菲加氢制烷基金刚烷的影响

doi:10.11949/0438-1157.20210303

摘要/Abstract

摘要：

以Pt为活性组分、经不同浓度草酸铝处理的USY分子筛为载体，制备了Pt/USY催化剂，并用于菲一步加氢饱和反应和加氢异构反应体系。由于金属活性位点Pt上易发生加氢反应，USY载体酸性位点上易发生异构反应和裂解反应，实验分别考察了Pt颗粒、载体的酸强度和酸量对菲转化率和产物分布的影响。结果表明，活性金属Pt颗粒尺寸及分散度直接影响菲加氢饱和产物分布；草酸处理后制备的催化剂Pt/0.05-USY、Pt/0.1-USY较未经酸处理的Pt/USY更利于菲加氢反应。全氢蒽是菲向目标产物烷基金刚烷转化的关键中间产物，异构产物烷基金刚烷生成需在USY分子筛Br?nsted酸位点完成；随着催化剂载体酸量和酸强度的降低，裂解反应程度迅速减弱；菲加氢反应最终产物以加氢饱和反应产物为主；使用Pt/0.1-USY催化剂异构反应产物烷基金刚烷收率为2.3%。

关键词: 催化作用, 加氢反应, 异构反应, 分子筛, 裂解反应

Abstract:

Pt/USY catalysts were prepared by using Pt as the active component and USY zeolite treated with different concentrations of oxalic acid as supports. For the investigation of concurrent hydrogenation saturation and isomerization, phenanthrene was chosen as a model compound. Since the hydrogenation reaction is prone to occur on the metal active site Pt and the isomerization reaction and cleavage reaction are prone to occur on the acid site of the USY carrier,the influence of the strength and concentration of acid sites on the phenanthrene conversion and product distribution was investigated. The particle size and dispersion of Pt sites affect the conversion rate of phenanthrene, which is faster over Pt/0.05-USY and Pt/0.1-USY than over Pt/USY catalysts. Perhydroanthracene is the key intermediate in the hydrogenation of phenanthrene to alkyl adamantane. The Br?nsted acid sites of the support promote the isomerization of alkyl adamantane. The formation of the isomer alkyl adamantane needs to be completed at the Br?nsted acid site. While decreasing the content and the strength of acid site in USY, the cracking reaction is inhibited which enhances the phenanthrene hydrogenation reaction to yield more hydrogenation saturated products. The yield of alkyl amantadane was 2.3% using Pt/0.1-USY catalysts.

Key words: catalysis, hydrogenation reaction, isomerization reaction, molecular sieves, pyrolysis

中图分类号:

O 643.32

王学明,李晓红,李文英. 载体酸性对Pt/USY菲加氢制烷基金刚烷的影响[J]. 化工学报, 2021, 72(10): 5196-5205.

Xueming WANG,Xiaohong LI,Wenying LI. Effect of support acidity on hydrogenation of phenanthrene to alkyl adamantane over Pt/USY catalysts[J]. CIESC Journal, 2021, 72(10): 5196-5205.

图/表 15

图1 菲催化加氢反应高压釜

Fig.1 Autoclave of catalytic hydrogenation reaction

表1 菲加氢异构产物组成的简称与结构式

Table 1 Acronyms and structural formula of products in catalytic hydroisomerization of phenanthrene

简称	化合物	简称	化合物
PHE	菲	THP	四氢菲
DHP	二氢菲	OHP	八氢菲
PHP	全氢菲	PrA	1,3,5,6-四甲基金刚烷
OHA	八氢蒽	PrA	1,3-二甲基-5-乙基金刚烷
PHA	全氢蒽	PrA	1,3,5,7-四甲基金刚烷

图2 不同浓度草酸处理后USY的SEM照片

Fig.2 SEM images of USY after dealumination with oxalic acid

图3 不同浓度草酸脱铝后的USY的XRD谱图

Fig.3 XRD patterns of USY after dealumination with oxalic acid

表2 不同浓度草酸脱铝后分子筛晶体结构参数

Table 2 Structural parameters of USY treated with different concentration of oxalic acid

样品	结晶度/%	晶胞常数/nm	骨架Si/Al比
USY	100	2.451	5.59
0.05-USY	82	2.442	8.85
0.1-USY	68	2.436	13.05
0.2-USY	40	2.430	27.9
0.3-USY	—	—	—

图4 不同浓度草酸脱铝后USY分子筛的N2物理吸附等温曲线

Fig.4 Nitrogen physical adsorption isotherms of USY zeolite treated with different concentration of oxalic acid

表3 不同浓度草酸脱铝后USY的比表面积和孔容

Table 3 Specific surface area and pore volume of USY after dealumination with oxalic acid

样品	比表面积/(m²/g)			孔容 /(cm³/g)
样品	总比表面积	微孔	介孔	总孔容	微孔	介孔
USY	805	590	215	0.43	0.22	0.21
0.05-USY	682	465	217	0.39	0.18	0.21
0.1-USY	648	427	221	0.37	0.16	0.21
0.2-USY	326	162	164	0.27	0.07	0.20
0.3-USY	126	0	126	0.19	0	0.19

图5 不同浓度草酸脱铝后的USY的NH3-TPD曲线

Fig.5 NH3-TPD curves of USY after dealumination with oxalic acid

图6 不同浓度草酸脱铝后的USY的FT-IR谱图

Fig.6 FT-IR spectra of USY after dealumination with oxalic acid

表4 不同浓度草酸处理USY的酸性变化

Table 4 Changes of acidity of USY after dealumination with oxalic acid

样品	150℃		300℃		WB^③/ (μmol/g)	WL^③/ (μmol/g)
样品	B^①/(μmol/g)	L^①/(μmol/g)	B^②/(μmol/g)	L^②/(μmol/g)	WB^③/ (μmol/g)	WL^③/ (μmol/g)
USY	337.1	160.4	272.2	125.4	64.9	35.0
0.05-USY	268.1	152.1	205.0	117.5	63.1	34.6
0.1-USY	221.2	152.5	180.9	114.0	40.3	38.5
0.2-USY	101.0	61.6	74.7	53.5	26.3	21.2
0.3-USY	3.5	6.9	1.6	4.1	1.9	2.8

图7 不同浓度草酸脱铝后的Pt/USY催化剂的XRD谱图

Fig.7 XRD patterns of Pt/USY catalysts after dealumination treatment of oxalic acid with different concentration

图8 不同Pt/USY催化剂在菲加氢反应中的反应活性

Fig.8 Effect of Pt/USY catalysts treated with oxalic acid on the phenanthrene hydrogenation reaction

图9 不同Pt/USY催化菲加氢反应的产物分布

Fig.9 Effect of Pt/USY catalysts treated with oxalic acid on the products distribution of phenanthrene hydrogenation

表5 菲加氢裂解反应产物（SHC）收率随催化剂酸量变化

Table 5 Yield variation of cracking reaction products （SHC） with the acid amount of Pt/USY catalysts

样品	总酸/(μmol/g)	SHC 收率/%
样品	总酸/(μmol/g)	1 h	2 h	3 h	4 h	5 h	6 h	7 h	8 h
Pt/USY	497.5	20.2	68.1	79.5	84.5	86.5	87.9	89.5	91.6
Pt/0.05-USY	420.2	0	26.8	50.6	69.4	79.0	83.6	87.3	88.8
Pt/0.1-USY	373.7	4.7	37.7	49.0	56.1	58.4	61.3	64.4	64.5
Pt/0.2-USY	162.6	0	2.2	4.5	5.0	6.5	10.8.	11.2	11.5
Pt/0.3-USY	10.4	0	0	0	0	0	0	0	0

图10 菲在Pt/USY催化剂上反应网络

Fig.10 Reaction network of phenanthrene on Pt/USY catalysts

参考文献 34

1	孔京. 高能量密度燃料分子设计及定向合成机理的理论研究[D]. 天津: 天津大学, 2011.
	Kong J. Molecular design and mechanistic simulation on orientated synthesis of high energy density fuel[D]. Tianjin: Tianjin University, 2011.
2	Landa S, Macháček V. Sur l'adamantane, nouvel hydrocarbure extrait du naphte[J]. Collection of Czechoslovak Chemical Communications, 1933, 5: 1-5.
3	von R Schleyer P. A simple preparation of adamantane[J]. Journal of the American Chemical Society, 1957, 79(12): 3292.
4	Schwertfeger H, Fokin A, Schreiner P. Diamonds are a chemist’s best friend: diamondoid chemistry beyond adamantane[J]. Angewandte Chemie International Edition, 2008, 47(6): 1022-1036.
5	Chung H S, Chen C S H, Kremer R A, et al. Recent developments in high-energy density liquid hydrocarbon fuels[J]. Energy & Fuels, 1999, 13(3): 641-649.
6	Schneider A, Warren R W, Janoski E J. Formation of perhydrophenalenes and polyalkyladamantanes by isomerization of tricyclic perhydroaromatics[J]. Journal of the American Chemical Society, 1964, 86(23): 5365-5367.
7	顾彦龙, 杨宏洲, 邓友全. 室温离子液体中双环戊二烯加氢以及金刚烷合成[J]. 石油化工, 2002, 31(5): 345-348.
	Gu Y L, Yang H Z, Deng Y Q. Hydrogenation of dicyclopentadiene and synthesis of adamantane in ionic liquids[J]. Petrochemical Technology, 2002, 31(5): 345-348.
8	Brito L, Pirngruber G D, Guillon E, et al. Hydroconversion of perhydrophenanthrene over bifunctional Pt/H-USY zeolite catalyst[J]. ChemCatChem, 2020, 12(13): 3477-3488.
9	Wang L, Chen Y J, Jin S H, et al. Selective ring-shift isomerization in hydroconversion of fluorene over supported platinum catalysts[J]. Energy & Fuels, 2016, 30(4): 3403-3412.
10	周卫国, 吴旭洲. 煤焦油中蒽、菲、咔唑的精制及利用[J]. 煤化工, 2002, 30(1): 1-5, 39.
	Zhou W G, Wu X Z. Refinement and application of anthracene, phenanthrene and carbazole from coal tar[J]. Coal Chemical Industry, 2002, 30(1): 1-5, 39.
11	张香文, 邱立勤, 陶然, 等. 三氯化铝催化体系合成金刚烷[J]. 石油化工, 1999, 28(8): 546-548, 561.
	Zhang X W, Qiu L Q, Tao R, et al. Studies on the AlCl₃ catalyst systems for the synthesis of adamantane[J]. Petrochemical Technology, 1999, 28(8): 546-548, 561.
12	Saginayev A. Syntheses, geometrical and electronic structure of alkyladamantanes and their thermodynamic characteristic according to the density functional theory[J]. Science Journal of Chemistry, 2018, 6(4): 50.
13	Qian W H, Yoda Y, Hirai Y, et al. Hydrodesulfurization of dibenzothiophene and hydrogenation of phenanthrene on alumina-supported Pt and Pd catalysts[J]. Applied Catalysis A: General, 1999, 184(1): 81-88.
14	Leite L, Benazzi E, Marchal-George N. Hydrocracking of phenanthrene over bifunctional Pt catalysts[J]. Catalysis Today, 2001, 65(2/3/4): 241-247.
15	Xie Z L, Feng J, Zhao W, et al. Formation of NO_x and SO_x precursors during the pyrolysis of coal and biomass (Ⅳ): Pyrolysis of a set of Australian and Chinese coals[J]. Fuel, 2001, 80(15): 2131-2138.
16	Rollmann L D, Green L A, Bradway R A, et al. Adamantanes from petroleum with zeolites[J]. Catalysis Today, 1996, 31(1/2): 163-169.
17	Nie X, Janik M J, Guo X, et al. A computational investigation of ring-shift isomerization of sym-octahydrophenanthrene to sym-octahydroanthracene catalyzed by acidic zeolites[J]. Physical Chemistry Chemical Physics, 2012, 14(48): 16644-16653.
18	Benazzi E, Leite L, Marchal-George N, et al. New insights into parameters controlling the selectivity in hydrocracking reactions[J]. Journal of Catalysis, 2003, 217(2): 376-387.
19	郭建维, 米镇涛, 杨军. 沸石催化合成金刚烷[J]. 石油化工, 1998, 27(1): 34-37.
	Guo J W, Mi Z T, Yang J. Synthesis of adamantane on zeolite catalyst[J]. Petrochemical Technology, 1998, 27(1):36-39.
20	Wingert W S. G.C.-M.S. analysis of diamondoid hydrocarbons in Smackover petroleums[J]. Fuel, 1992, 71(1): 37-43.
21	Thibault-Starzyk F, Stan I, Abelló S, et al. Quantification of enhanced acid site accessibility in hierarchical zeolites — the accessibility index[J]. Journal of Catalysis, 2009, 264(1): 11-14.
22	王舒君, 刘璞生, 谢鑫, 等. 柠檬酸溶液中NaY分子筛的脱铝行为[J]. 分子催化, 2019, 33(4): 363-370.
	Wang S J, Liu P S, Xie X, et al. Dealumination behavior of zeolite NaY in citric acid solution[J]. Journal of Molecular Catalysis (China), 2019, 33(4): 363-370.
23	田志坚, 梁东白, 林励吾. 烃类加氢异构化及加氢异构裂化催化剂的研究开发[J]. 催化学报, 2009, 30(8): 705-710.
	Tian Z J, Liang D B, Lin L W. Research and development of hydroisomerization and hydrocracking catalysts in Dalian Institute of Chemical Physics[J]. Chinese Journal of Catalysis, 2009, 30(8): 705-710.
24	孙晨晨. 柴油芳烃加氢饱和及其选择性开环的研究[D]. 西安: 西安石油大学, 2016.
	Sun C C. Study on hydrogenation saturation and selective ring opening of diesel aromatics[D]. Xi'an: Xi'an Shiyou University, 2016.
25	Corma A, Martı́nez A, Martı́nez-Soria V. Hydrogenation of aromatics in diesel fuels on Pt/MCM-41 catalysts[J]. Journal of Catalysis, 1997, 169(2): 480-489.
26	Kubička D, Kumar N, Venäläinen T, et al. Metal-support interactions in zeolite-supported noble metals: influence of metal crystallites on the support acidity[J]. The Journal of Physical Chemistry B, 2006, 110(10): 4937-4946.
27	蒋端六, 蒋持衡. C₅馏份的综合利用: 超强酸合成金刚烷[J]. 江苏化工, 1996, 24(6): 25-26.
	Jiang D L, Jiang C H. Comprehensive utilization of C₅-fraction-synthesis of adamantane by ultrastrony acid catalyst[J]. Jiangsu Chemical Industry, 1996, 24(6): 25-26.
28	Pu X, Liu N W, Shi L. Acid properties and catalysis of USY zeolite with different extra-framework aluminum concentration[J].Microporous and Mesoporous Materials, 2015, 201: 17-23.
29	Emeis C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141(2): 347-354.
30	Wang Z L, Hu H S, von Szentpály L, et al. Understanding the uniqueness of 2p elements in periodic tables[J]. Chemistry — A European Journal, 2020, 26(67): 15558-15564.
31	Wang J, Li Q Z, Yao J D. The effect of metal-acid balance in Pt-loading dealuminated Y zeolite catalysts on the hydrogenation of benzene[J]. Applied Catalysis A: General, 1999, 184(2): 181-188.
32	Luo M J, Wang Q F, Li G Z, et al. AlCl₃-promoted MCM-41-supported platinum catalysts with high activity and sulfur-tolerance for tetralin hydrogenation: effect of Pt-Al interaction[J]. Catalysis Communications, 2013, 35: 6-10.
33	Lai W C, Song C S, van Duin A, et al. Ring-shift isomerization of sym-octahydrophenanthrene into sym-octahydroanthracene. Effects of zeolite catalysts and equilibrium compositions[J]. Catalysis Today, 1996, 31(1/2): 145-161.
34	Beltramone A R, Resasco D E, Alvarez W E, et al. Simultaneous hydrogenation of multiring aromatic compounds over NiMo catalyst[J]. Industrial & Engineering Chemistry Research, 2008, 47(19): 7161-7166.

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