A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal cry...A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.展开更多
Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are prefere...Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are preferentially adsorbed in the supercages of the zeolite at low Xe pressure (less than a few atmosphere), while Xe atoms can penetrate into the two-dimensional sinusoidal channels at high Xe pressure. Exchange of xenon at the different adsorption sites in the same supercage, i.e. xenon atoms in the two pockets and those in the central part of the supercage, was confirmed at 145 K by two-dimensional (2D) 129Xe NMR exchange spectroscopy. The time scale for the exchange is about several milliseconds.展开更多
The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid c...The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid(i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22(i.e., MCM-22-IL)was characterized by FTIR, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene(I/O) were investigated to correlate with surface features of MCM-22-IL. Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene(I/O) was significantly improved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.展开更多
The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure o...The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure on the performance of MCM-22 zeolite for catalytic skeletal isomerization of 1-hexene was examined. The experimental results showed that at a steam treatment temperature of 500℃, a reaction temperature of 270℃, a space velocity of 1.0 h-1 and a reaction pressure of 0.2 MPa, the MCM-22 zeolite exhibited excellent performance for catalytic skeletal isomerization of 1-hexene with the i-hexene yield reaching 66.15%. Compared with other commonly used molecular sieve catalysts, the MCM-22 zeolite catalyst exhibited better catalytic performance for skeletal isomerization of 1-hexene.展开更多
Hydroisomerization catalysts Pt/ZSM-22, Pt/ZSM-23, and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22, ZSM-23, and intergrowth zeolite ZSM-22/ZSM-23, respectively. The typical physicochemical properties of ...Hydroisomerization catalysts Pt/ZSM-22, Pt/ZSM-23, and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22, ZSM-23, and intergrowth zeolite ZSM-22/ZSM-23, respectively. The typical physicochemical properties of these catalysts were characterized by X-Ray Diffraction (XRD), N2 absorption-desorption, Pyridine-Fourier Transform Infrared (Py-FTIR), Transmission Electron Microscopy (TEM), X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM) and NH3- Temperature Programmed Desorption (NH3-TPD), and the performance of these catalysts in n-dodecane hydroisomerization was evaluated in a continuous down-flow fixed bed with a stainless steel tubular reactor. The characterization results indicated that the intergrowth zeolite ZSM-22/ZSM-23 possessed the dual structure of ZSM-22 and ZSM-23, and the catalyst Pt/ZSM-22/ZSM-23 had similar pores and weak acidity to Pt/ZSM-22 and Pt/ZSM-23 catalysts. Moreover, Pt/ZSM-22/ZSM-23 catalyst showed a high selectivity in hydroisomerization of long chain n-alkanes to mono-branched isomers. The evaluation results for n-dodecane hydroisomerization indicated that the activity of Pt/ZSM-22/ZSM-23 was the lowest, while the hydroisomerization selectivity was the highest among the three catalysts. The maximum yield of i-dodecane product was 68.3% over Pt/ZSM-22/ZSM-23 at 320 ℃.展开更多
MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phe...MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phenol.展开更多
基金the financial supports from the National Natural Science Foundation of China(22322803,22178059,22208054,22221005,22072019)Key Technologies Innovation and Industrialization Projects of Fujian Province(2022G031)Qingyuan Innovation Laboratory(00121002,00523005)。
文摘A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29873065).
文摘Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are preferentially adsorbed in the supercages of the zeolite at low Xe pressure (less than a few atmosphere), while Xe atoms can penetrate into the two-dimensional sinusoidal channels at high Xe pressure. Exchange of xenon at the different adsorption sites in the same supercage, i.e. xenon atoms in the two pockets and those in the central part of the supercage, was confirmed at 145 K by two-dimensional (2D) 129Xe NMR exchange spectroscopy. The time scale for the exchange is about several milliseconds.
基金Supported by the National Natural Science Foundation of China(21576168,21276163)
文摘The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid(i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22(i.e., MCM-22-IL)was characterized by FTIR, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene(I/O) were investigated to correlate with surface features of MCM-22-IL. Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene(I/O) was significantly improved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.
文摘The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure on the performance of MCM-22 zeolite for catalytic skeletal isomerization of 1-hexene was examined. The experimental results showed that at a steam treatment temperature of 500℃, a reaction temperature of 270℃, a space velocity of 1.0 h-1 and a reaction pressure of 0.2 MPa, the MCM-22 zeolite exhibited excellent performance for catalytic skeletal isomerization of 1-hexene with the i-hexene yield reaching 66.15%. Compared with other commonly used molecular sieve catalysts, the MCM-22 zeolite catalyst exhibited better catalytic performance for skeletal isomerization of 1-hexene.
基金the financial supports form Petrochina(050508-04-02)the National Natural Science Foundation of China(No.21073235,and 20833011)
文摘Hydroisomerization catalysts Pt/ZSM-22, Pt/ZSM-23, and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22, ZSM-23, and intergrowth zeolite ZSM-22/ZSM-23, respectively. The typical physicochemical properties of these catalysts were characterized by X-Ray Diffraction (XRD), N2 absorption-desorption, Pyridine-Fourier Transform Infrared (Py-FTIR), Transmission Electron Microscopy (TEM), X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM) and NH3- Temperature Programmed Desorption (NH3-TPD), and the performance of these catalysts in n-dodecane hydroisomerization was evaluated in a continuous down-flow fixed bed with a stainless steel tubular reactor. The characterization results indicated that the intergrowth zeolite ZSM-22/ZSM-23 possessed the dual structure of ZSM-22 and ZSM-23, and the catalyst Pt/ZSM-22/ZSM-23 had similar pores and weak acidity to Pt/ZSM-22 and Pt/ZSM-23 catalysts. Moreover, Pt/ZSM-22/ZSM-23 catalyst showed a high selectivity in hydroisomerization of long chain n-alkanes to mono-branched isomers. The evaluation results for n-dodecane hydroisomerization indicated that the activity of Pt/ZSM-22/ZSM-23 was the lowest, while the hydroisomerization selectivity was the highest among the three catalysts. The maximum yield of i-dodecane product was 68.3% over Pt/ZSM-22/ZSM-23 at 320 ℃.
文摘MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phenol.