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FUEL PROCESSING TECHNOLOGY · 2022 · IF 8.129

Unpredictable properties of industrial HY zeolite for tetralin hydrocracking

Jiayao Qi,Yanni Guo,Hanqiong Jia,Binbin Fan,Hang Gao,Bo Qin,Jinghong Ma,Yanze Du,Ruifeng Li

The commercial Y zeolites are widely used in catalytic cracking and hydrocracking in industry, the efficient hydrocracking of polycyclic aromatics is a challenging task in petroleum and coal refining. The acidic zeolite in the hydrocracking bi-functional catalyst dominates largely the product selectivity, so understanding the independent effect of acid sites is favorable to the design of the catalyst. Herein, five industrial HY zeolites with different ratios of Si/Al were applied to tetralin hydrocracking to produce high-value benzene, toluene, and xylenes (BTX) in a high-pressure fixed bed reactor . The result indicated that mesoporous HUSY not only improved the catalytic activity but also exhibited longer-term stability compared with micropore HY. Interestingly, tetralin conversion in the hydrocracking showed a high-similar value when the Si/Al ratio of the zeolites is above 26 with almost identical porous structure , regardless of the distribution of acidity. And the yield of products is associated with the acidity of the HY zeolites, the lower the Si/Al ratio is, the more favorable the monocyclic aromatic hydrocarbons form. Therefore, it is beneficial for the industrial process to reduce the zeolite post-treatment procedure which achieves the high activity and BTX yield in the hydrocracking of tetralin and to abate the cost consumption, although it is still impractical to get rid of the trial-error scheme for the designing of an efficient catalyst in practice.

CAS / MDL: 119-64-2
研究领域: 催化化学 · 石油加工工程
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MICROPOROUS AND MESOPOROUS MATERIALS · 2022 · IF 5.876

NiMo/C-HY catalyst prepared from doping zeolite slurry in a superabsorbent polymer for DBT and 4,6-DMDBT hydrodesulfurization

Zhiheng Wang,Yanyan Liu,Xin Li,Ruiyao Gao,Jiong Sun,Jiankun Liu,Songdong Yao

This study utilized the swelling properties of superabsorbent polymers (SAP) to adsorb zeolite sols and slurries to construct C-HY composites. The synthesized C-HY composites proved to be effective supports for NiMo catalysts in the hydrodesulfurization (HDS) of dibenzothiophene ( DBT ) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT). XRD , BET, SEM, TG, NH 3 -TPD, FTIR, H 2 -TPR, TEM and XPS were used to characterization the texutural structure, acidity and metal distribution of prepared NiMo/C-HY catalysts. By combining zeolite slurries with SAPs, HY can be efficiently incorporated into carbon substrate structure in three dimensions (3D), thereby changing the structural characteristics, morphology, acidity, and metal distribution of HDS catalysts. The conversion of DBT decreases sequentially: NiMo/C-HY-s > NiMo/C-HY-h > NiMo/C-HY-p > NiMo/C-HY-c, and the conversion of 4,6-DMDBT decreased sequentially: NiMo/C-HY-s > NiMo/C-HY-p > NiMo/C-HY-h ≫ NiMo/C-HY-c. The introduction of HY into the carbon support can increase the HDS reaction rate of NiMo/C by more than 1.2–1.5 times. The intrinsic reaction activity of NiMo/C-HY-s can even exceed that of traditional NiMo/Al 2 O 3 catalysts. Based on the same Mo loading amount, the HDS activity of NiMo/C-HY-s is twice that of NiMo/Al 2 O 3 in DBT HDS and 1.1–1.5 times that of NiMo/Al 2 O 3 in 4,6-DMDBT HDS. It is thought that HY in carbon composites promotes C–S bond cleavage of sulfur-containing molecules in DBT HDS. The unique dispersion of Mo species induced by HY favors the formation of highly stacked NiMoS active phases, which may be the crucial in 4,6-DMDBT HDS.

研究领域: 催化化学 · 材料科学 · 能源化工
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APPLIED CATALYSIS A-GENERAL · 2018 · IF 4.521

Conversion of fructose into furfural or 5-hydroxymethylfurfural over HY zeolites selectively in γ-butyrolactone

Liqin Wang,Heqin Guo,Qilong Xie,Jungang Wang,Bo Hou,Litao Jia,Jinglei Cui,Debao Li

Furfural is one of the most valuable biomass platform compounds which is typically prepared from hemicellulose. Conversion of cellulose and its derived hexoses, which are the most abundant resource in nature, to furfural, is a big challenge. The amount of the reactive form (fructofuranose) which was beneficial to the formation of furfural and HMF, was increased when the solvent transformed from water to γ-butyrolactone (GBL)-water. The GBL promoted the adsorption of fructose on HY. The transfer of fructose from the solution to the channels of HY was enhanced with the introducing of GBL in solvent. The HY zeolite with apertures of 7.4 Å was found to promote the formation of acyclic fructose from cyclic fructose (8.6 Å) in the synergy with GBL. The Brønsted acid sites in the channels of HY favored the selective cleavage of the C C bond in acyclic fructose to xylose, and promoted the following dehydration of xylose to furfural, simultaneously. The furfural yield was increased while the 5-hydroxymethylfurfural (HMF) yield was decreased with the decrease of the Brønsted acid sites density. The maximum furfural yield was 37.8% over HY-3, while the maximum HMF yield was 69.2% over HY-1 in the conversion of fructose in GBL-water solvent. In addition, the etherification of HMF was the main factor for the low HMF yield and carbon balance in fructose conversion in GBL-water solvent.

研究领域: 化学工程 · 生物质转化
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Molecular Catalysis · 2022 · IF 5.089

Constructing optimally hierarchical HY zeolite for the synthesis of high-energy-density tricyclic hydrocarbon fuel

Huiying Wang,Xiangwen Zhang,Guozhu Li

In this work, a tricyclic fuel possessing high energy density and low freezing point has been synthesized via directional alkylation of naphthalene with cyclohexene. A hierarchical HY zeolite with well-defined micro/mesoporous framework was prepared by an alkali-treatment method to efficiently catalyze the reaction. Both porosity and acidity of HY zeolite were optimized by tuning NaOH concentration to maintain the active acid sites and increase their accessibility. The optimally hierarchical HY catalyst (0.5 HY) exhibited higher catalytic activity and good recycling stability. As a result, the tricyclic fuel was produced in high yield, which possesses an energy density of 42.38 MJ/L and a freezing point of < -75 °C. This work provides a straightforward reaction route and an efficient catalyst for the production of a high energy density tricyclic fuel using readily available raw materials.

CAS / MDL: 12125-02-9 1310-73-2
研究领域: 化学工程 · 能源科学
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ACS Omega · 2021 · IF 3.512

Highly Efficient Hydroisomerization of Endo-Tetrahydrodicyclopentadiene to Exo-Tetrahydrodicyclopentadiene over Pt/HY

Wenke Wang,Jie Zhao,Dandan Jia,Zhaolin Fu,Enhui Xing,Zhongpeng Zhu,Rui Yan,Zhiping Tao,Yibin Luo,Xingtian Shu

The fast deactivation caused by serious formation of coke is a major challenge in catalytic isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) into exo-tetrahydrodicyclopentadiene (exo-THDCPD) over the HY zeolite. In order to suppress the coke formation for the isomerization process, the conventional HY zeolite was modified with Pt at 0.3 wt %. Then, the hydroisomerization of endo-THDCPD into exo-THDCPD was evaluated over a fixed-bed reactor. The catalytic stability of Pt/HY was greatly enhanced in comparison to that of the HY zeolite. The Pt/HY catalyst provided 97% endo-THDCPD conversion and 96% selectivity for exo-THDCPD without deactivation after 100 h. Moreover, the formation mechanism of coke on the HY zeolite during the isomerization process was proposed based on the results of the coke analysis. It was indicated that the coke was generated from the oligomerization and condensation of olefin species, which originated from the β-scission reaction or hydride transfer reaction of intermediates. The lower coke formation over Pt/HY was attributed to the lower amount of coke precursors, which could be hydrogenated by activated H2 over Pt sites. Therefore, Pt on Pt/HY and H2 were two crucial factors in efficiently enhancing the catalytic stability of the HY zeolite for this isomerization reaction.

CAS / MDL: 108-87-2
研究领域: 催化化学 · 材料科学 · 石油化工
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Catalysts · 2025 ·Vol. 15 ·期 5 ·413 · IF 4

Constructing Pt/Hierarchical HY Bifunctional Catalysts for Selective Hydroisomerization of Phenanthrene to Alkyl-Adamantanes

Nan Jiang,Xiaopo Niu,Danni Liu,Kaige Zhang,Zhen Guo,Yue Qin,Wenli Zhao,Xiangwen Zhang,Qingfa Wang

Designing bifunctional catalysts for efficient hydroisomerization of phenanthrene to alkyl-adamantane is a great challenge for producing high-density fuels. Herein, a bifunctional Pt catalyst was fabricated by developing hierarchical H-MSY-T zeolites with an NOA-co strategy. The influence of different mesopore template agents on the hierarchical structure of H-MSY-T zeolite was investigated. Effective regulation of pore structure and acid distribution of zeolites was achieved by adjusting the templating agents. The block copolymer P123 promoted the formation of mesoporous structures via self-assembly with a large mesopore centered at 8 nm. Large mesoporous structure and suitable distribution of Bronsted acid boosted the hydroisomerization of phenanthrene. The highest alkyl-adamantane yield of 45.9 wt% was achieved on the Pt/MSY-P1 catalyst and a reaction network of hydroisomerization was proposed. This work provides guidance to design highly selective bifunctional catalysts for the one-step hydroconversion of tricyclic aromatic hydrocarbons into high-density fuels.

研究领域: 化学工程 · 催化材料
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AICHE JOURNAL · 2022 ·Vol. 68 ·期 11 ·e17831 · IF 4.167

Detailed understanding on thermodynamic and kinetic features of phenanthrene hydroprocessing on Ni-Mo/HY catalyst

Chong Peng,Peng Liu,Zhiming Zhou,Xiangchen Fang,Yun-Xiang Pan

Phenanthrene hydrogenation is a key reaction for improving the quality of gasoline and diesel. Herein, we conduct detailed thermodynamic and kinetic analyses for phenanthrene hydrogenation on a Ni-Mo/HY catalyst. We establish a comprehensive reaction network for phenanthrene hydrogenation, and calculate equilibrium constant, rate constant, adsorption constant, activation energy barrier, and reaction energy for each step in the reaction network. All of the steps in the reaction network are revealed to be exothermic. A kinetic model with 28 parameters is constructed for phenanthrene hydrogenation. The deviation of the product yields calculated by the kinetic model from those obtained in experiments is less than 4.5%, indicating the reasonability and accuracy of the kinetic model. The most favorable pathway for phenanthrene hydrogenation is demonstrated to be phenanthrene → tetrahydrophenanthrene → sym-octahydrophenanthrene → 5,6-butyl-tetrahydronaphthalene → tetralin. These results are helpful for efficiently tuning catalyst properties and optimizing reaction conditions for enhancing phenanthrene hydrogenation.

研究领域: 化学工程 · 催化科学
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MATERIALS CHEMISTRY AND PHYSICS · 2024 · IF 4.3

Catalytic benzylation of arenes using metal-ion modified HY zeolites for sustainable synthesis

Meihuan Lu,Satish Gudala,Zheng Liu,Archi Sharma,Xinyu Liu,Jianxin Yang

Microporous zeolites are commonly employed as catalysts for the benzylation of arenes and benzyl alcohol. However, their catalytic efficiency is often compromised by diffusion limitations, particularly in reactions involving larger arenes. In this study, we developed metal-ion modified HY zeolites using Zn, Mg, and Ni as dopants and investigated their catalytic performance in the benzylation of a range of arenes, including toluene, benzene, mesitylene, p-xylene and with benzyl alcohol (BzOH). The structural and acidic properties of the modified HY zeolites were characterized using a combination of techniques including scanning electron microscopy (SEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms, Fourier-transform infrared (FTIR) spectroscopy, ammonia temperature-programmed desorption (NH₃-TPD), and proton magic angle spinning nuclear magnetic resonance ( 1 H MAS NMR) spectroscopy. The presence of catalytically active Brønsted acid sites (BAS) was detected by 1H MAS NMR spectroscopy and it was demonstrated that the HY zeolite's acidity is considerably modulated by the addition of metal ions. The catalytic evaluations indicated that the metal-ion modified HY zeolites exhibited superior activity compared to unmodified HY zeolite, with the catalytic performance following the order Zn/HY > Ni/HY > Mg/HY > HY for the benzylation of benzyl alcohol with mesitylene. Further investigation into the mechanism revealed that the synergistic effect of metal ions and acidity plays a crucial role in enhancing the accessibility of arenes to the surface catalytic sites and thereby improving catalytic performance. These findings underscore the importance of the metal-acidity synergy in optimizing the catalytic efficacy of modified HY zeolites for selective benzylation reactions.

研究领域: 化学工程 · 催化科学
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2023 ·Vol. 40 ·期 9 ·2149-2158 · IF 2.7

Hydrogenation of dimethyl 2,5-furandicarboxylate to dimethyl tetrahydrofuran-2,5-dicarboxylate over Ru/HY

Li Chengfeng,Lyu Qishen,Li Zheng,Yang Shuliang,Sun Yong,Tang Xing,Zeng Xianhai,Lin Lu

The hydrogenation of biomass-based furan compounds is an important step for the catalytic valorization of biobased chemicals. In this work, Ru-based catalysts supported on different supports, such as HY, MgO and Amberlyst-15, were prepared and estimated for the hydrogenation of dimethyl 2,5-furandicarboxylate (FDMC). Among them, Ru/HY provided a desirable yield of 99.4% for tetrahydrofuran-2,5-dicarboxylic acid dimethyl ester (THFDMC) under 90 °C and 3 MPa H 2 . Based on catalyst characterization, Ru/HY could offer more surface Ru 0 species and carbon radical intermediates than other catalysts, which could largely favor the activation of hydrogen and then promote the hydrogenation of FDMC over Ru/HY.

CAS / MDL: 39389-20-3 1309-48-4
研究领域: 催化化学 · 可再生资源化工
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RENEWABLE ENERGY · 2022 · IF 8.634

Efficient and stable SiO2-encapsulated NiPt/HY catalyst for catalytic cracking of β-O-4 linkage compound

Wenjing Song,Mengxue Song,Wenqing Cai,Weichu Li,Xingmao Jiang,Weiping Fang,Weikun Lai

Development of highly active and stable catalyst for C–O bonds cracking is important in biomass conversion , in this work, we report a SiO 2 -encapsulated NiPt/HY core-shell catalyst for phenethoxybenzene (PEB) catalytic cracking . The as-grown silica shell with defined pores serves as a ‘storage’ to enhance local concentration of PEB and intermediate isomers and promotes catalytic cracking on NiPt/HY core. With the increase of silica shell thickness from 0 to 40 nm, PEB reaction rate has increased more than five times, and the major cracking product selectivity is raised to above 90%, which is attributed to the continuous conversion of PEB isomers within the shell. This designed structure endows the NiPt/HY@SiO 2 with a high activity and no obvious deactivation in PEB cracking to corresponding phenol and aromatics. The outstanding performance benefit from the enrichment effect on the unique core-shell structure, as well as the moderate acidity originated from silica regulation. This work can be extended to the modulation of microenvironment to promote the catalytic behavior of core-shell catalysts.

研究领域: 催化化学 · 材料科学 · 生物质能
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Pilot-scale validation and novel design of reactive distillation with HY@SiC foam catalytic packing for cyclohexyl acetate production

Zhengkun Hou,Qiuyan Ding,Xueli Geng,Hong Li,Chang Shu,Xin Gao

For reactive distillation (RD) process limited by the separation efficiency of gas–liquid mass transfer, if the physical size of the alternating operation in reaction and separation can be further reduced, it would greatly promote the efficiency of the RD process. For this purpose, a structured HY@SiC catalytic packing was developed in which the gas–liquid mass transfer separation process and the catalytic reaction occurred simultaneously on its surface. The HY@SiC catalytic packing was used in a pilot-scale column for experimental study on production of cyclohexyl acetate (CA) by RD to verify the performance of the catalytic packing for the first time. Furthermore, a RD model based on the HY@SiC catalytic packing was established based on the reaction kinetics of HY zeolite catalyst obtained in this work. Finally, a novel RD process with double recycle stream for CA production was proposed, which will be optimized design with TAC minimize as the optimization objective based on sequential iterative algorithm.

CAS / MDL: 110-83-8
研究领域: 化学工程 · 催化反应工程
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Catalysts · 2022 ·Vol. 12 ·期 6 ·640 · IF 4.501

Modification of the Acidic and Textural Properties of HY Zeolite by AHFS Treatment and Its Coke Formation Performance in the Catalytic Cracking Reaction of N-Butene

Xu Lu,Chenhao Wei,Liang Zhao,Jinsen Gao,Chunming Xu

Coke formation on n-butene cracking catalyst is the main reason for the reducing of its lifetime. To study the effects of acidity and textural properties on the coke formation process, a series of HY zeolite-type catalysts were prepared by ammonium hexafluorosilicate treatment (AHFS). NH3-TPD and Py-IR-TPD were used to systematically study the change law of zeolite acidity. It was found that with the increase of AHFS concentration, the acid density decreased, whereas the ratio of Brønsted acid to Lewis acid first increased and then decreased. Meanwhile, the percentage of Brønsted acid inside the supper cages increased and the strength of Brønsted acid increased with the degree of dealumination. Combined with in situ IR study on coke formation, the relationship between coking and acid site was revealed. It was found that the rate of coke formation on zeolites was affected by acid density, which is the rate of coke formation decreased with the decline of acid density. When the acid density remains at the same level, it was the acid strength that determined the coke formation rate—the stronger the acid strength, the faster the coke formation rate.

研究领域: 催化化学 · 材料科学
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