Effect of support acidity on hydrogenation of phenanthrene to alkyl adamantane over Pt/USY catalysts

doi:10.11949/0438-1157.20210303

Abstract

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

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

CLC Number:

O 643.32

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.

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.

Figures/Tables 15

Fig.1 Autoclave of catalytic hydrogenation reaction

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

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

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

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	—	—	—

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

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

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

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

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

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

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

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

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

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

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