Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,th...Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,the catalysts were prepared successfully with different methods to improve the catalytic performance.The conversion of 0.01%Pt1@CeOx/SAPO-11 prepared by co-calcination method(0.01%Pt1@CS-c)is 71.4%,25%higher than the other prepared by precipitation method.The turnover frequency per active surface platinum site(TOFPt)of 0.01%Ptl@CS-c is as high as 13115 h^(-1).Revealed by the X-ray photoelectron spectroscopy(XPS)results,the quality of phase boundary/intersurface between ceria and zeolite is found significantly different.The conjunction quality of phase boundary directly affects the spillover rate of intermediate species,which further leads to an apparent activity difference.In addition,the possible role of ceria in the reaction is discussed,rather than just as a carrier for the active metal atoms.展开更多
Hierarchical SAPO-11, featuring both micropore and mesopore channels, demonstrates an outstanding performance in high-octane gasoline production. In this work, we propose an economic and effective approach to directly...Hierarchical SAPO-11, featuring both micropore and mesopore channels, demonstrates an outstanding performance in high-octane gasoline production. In this work, we propose an economic and effective approach to directly fabricate hierarchical SAPO-11 molecular sieve from natural kaolin, eliminating the need for mesoporogens. The systematic characterization results show that the kaolin-derived SAPO-11 possesses abundant micro-mesoporous structure and more Brønsted (B) acid sites on the external surface in contrast with the conventional SAPO-11 prepared employing silica sol as silicon source as well as SAPO-11 synthesized with the assist with of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (F127). The analysis of the formation process reveals that the kaolin not only provides silicon source for the SAPO-11 crystal growth, but also offers confined environment for crystal growth along the preferential orientation, resulting in the generation of the microporous and mesoporous structure. Benefiting from these unique properties, the kaolin-derived Pt/SAPO-11 exhibits considerably improved selectivity for di-branched C8 isomers in n-octane hydroisomerization.展开更多
By means of X-ray diffraction（XRD）, N2 adsorption-desorption, Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, NH3-temperature（NH3-TPD）, Py-infrared（Py-IR） and thermogravime...By means of X-ray diffraction（XRD）, N2 adsorption-desorption, Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, NH3-temperature（NH3-TPD）, Py-infrared（Py-IR） and thermogravimetry-differential scanning calorimetry（TG/DTA） techniques, the influences of Ce on the structure, acidity, stability and hydroisomerization performance of Ni-HPW/MCM-48 and Ni-HPW/Ce-MCM-48 catalysts were studied. The results showed that introduction of appropriate content of Ce into MCM-48 could improve the crystallinity, acidity and stability of mesoporous silica. The acidity and stability of the Ni-HPW/Ce-MCM-48 catalyst was also increased. Besides, the catalytic performance of the Ni-HPW/Ce-MCM-48 catalyst for n-heptane hydroisomerization was promoted. The conversion and selectivity of the Ni-HPW/Ce-MCM-48 catalyst reached 41% and 91% respectively at the preparation conditions of 4 wt.% Ni, 20 wt.% HPW, 0.03 Ce/Si molar ratio.展开更多
Y-β zeolite composites were hydrotherrnally synthesized by using high silica Y zeolite as the precursor and characterized by XRD, N2 adsorption, SEM and IR spectra of pyridine. The result showed that the N2 adsorptio...Y-β zeolite composites were hydrotherrnally synthesized by using high silica Y zeolite as the precursor and characterized by XRD, N2 adsorption, SEM and IR spectra of pyridine. The result showed that the N2 adsorption-desorption isotherm of the zeolite composites had a distinct hysteresis loop, and the SEM result showed that the zeolite composites had a different morphology from Y, β and the corresponding physical zeolite mixture. The acid catalytic performance of the zeolite composite catalysts was investigated in the hydrocracking and hydroisomerization of n-octane, and the results showed that the composite materials exhibited an excellent hydrocracking activity and good hydroisomerization performance. The yield of i-C4 over the zeolite composite catalyst was 4.45% higher than that on the corresponding zeolite mixture in the n-octane hydrocracking process at 553 K. The isomerization ability of n-octane over the composite catalyst was 3.6 fold that of the corresponding mixture at 503 K.展开更多
Zinc-modified Pt/SAPO-11 catalysts were prepared by incipient wetness impregnation and assessed in the hydroisomerization of n-octane.Their physicochemical properties were investigated using powder X-ray diffraction,s...Zinc-modified Pt/SAPO-11 catalysts were prepared by incipient wetness impregnation and assessed in the hydroisomerization of n-octane.Their physicochemical properties were investigated using powder X-ray diffraction,scanning electron microscopy,nitrogen adsorption-desorption,pyridine-adsorbed infrared spectroscopy,temperature-programmed desorption of NH3,temperature-programmed reduction of hydrogen,temperature-programmed desorption of hydrogen,transmission electron microscopy,and X-ray photoelectron spectroscopy.The addition of zinc resulted in high dispersion of platinum.Zinc acted as a competitive adsorbent,changed the location of platinum.The catalyst with a zinc loading of 0.5%gave the highest selectivity to dimethylhexanes,but the conversion was lower than those achieved with the other catalysts.Dimethylhexanes have large molecular diameters,and therefore their diffusion may be difficult.This weakens the catalytic activity of the zinc-modified catalysts and lowers the n-octane conversion.展开更多
A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,t...A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,the performance of the obtained bifunctional catalysts toward the hydroisomerization of n-dodecane was examined.The prepared samples were characterized by XRD,SEM,BET,XRF,Py-IR,and solid-state NMR.From the results,it was found that the high crystallinity and uniform morphology were retained after the post-treatment and that more(002)crystal faces were exposed,which was beneficial since more acid sites were provided.More importantly,the total Bronsted acid sites and the ratio(Ra)of the micropore area to the total surface area were optimized by this method.Thus,the catalytic performance was enhanced significantly,and the prepared Pt-SAPO-11-10%catalyst had the highest i-dodecane yield of 80.1%compared to 55.3%of Pt-SAPO-11.Expectedly,this facile and cost-effective method is promising for the hydroisomerization of normal paraffin in the production of lubricant base oils.展开更多
A series of Pt catalysts supported on the Hβ-zeolite that is ion-exchanged with the rare earth metal ions of Ce（III） and La（III）,are prepared by impregnation,characterized by inductively coupled plasma （ICP）,X-...A series of Pt catalysts supported on the Hβ-zeolite that is ion-exchanged with the rare earth metal ions of Ce（III） and La（III）,are prepared by impregnation,characterized by inductively coupled plasma （ICP）,X-ray diffraction （XRD）,BET,temperature-programmed desorption of ammonia （NH3-TPD）,temperature-programmed reduction of hydrogen （H2-TPR） and H2-chemisorption techniques,and evaluated in the hydroisomerization of n-heptane with an atmospheric fixed-bed reactor.The reaction temperature,time on stream,space velocity,and the ratio of H2/n-heptane are changed to get the optimal conditions.The Ce（III） and La（III）-exchanged Hβ-zeolites exhibit higher selectivity for isomerized products than the neat Hβ-zeolite.Moreover,the Ce（III）-exchanged catalysts give higher conversions of n-heptane,whereas the La（III）-exchanged ones do not show any improvement in con-version.Under optimal conditions,the catalyst with 0.4% （by mass） Pt and 0.5% （by mass） Ce loading presents very high selectivity of isomerized products of 95.1% coupled with high n-heptane conversion of 68.7%.Effects of the ion-exchange of Ce（III） and La（III） on the catalytic performance are discussed in relation with the physico-chemical properties of catalysts.展开更多
The bimetallic NiCu/SAPO-11 catalysts were prepared by co-impregnation, sequential impregnation, coprecipitation, and mechanical mixing methods. Powder X-ray diffraction, nitrogen adsorption-desorption,temperature-pro...The bimetallic NiCu/SAPO-11 catalysts were prepared by co-impregnation, sequential impregnation, coprecipitation, and mechanical mixing methods. Powder X-ray diffraction, nitrogen adsorption-desorption,temperature-programmed desorption of ammonia, transmission electron microscopy, temperatureprogrammed reduction of hydrogen, and X-ray photoelectron spectroscopy were used to characterize the physicochemical properties of the catalysts. The catalytic performance of the catalysts was assessed by the hydroisomerization of n-octane. Results indicated that the conversion of n-octane and selectivity to n-octane isomers were related to the preparation methods of the catalysts. The catalysts with Ni-Cu alloy effectively restrained the hydrogenolysis reaction that decreases the selectivity of isomerization. The catalyst prepared by the mechanical mixing of NiO and CuO hardly formed Ni-Cu alloy, showing obvious hydrogenolysis and low selectivity to n-octane isomers. The unbalance between the metal and acid sites resulted in the low conversion of n-octane and selectivity to n-octane isomers. Among all the catalysts,the catalyst prepared by the co-impregnation method exhibited high catalytic activity and selectivity to n-octane isomers.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
Hydro isomerization of linear alkanes to branched isomers is an important petrochemical process for production of gasoline with high octane number.Non-noble metal bifunctional catalysts used in this process always suf...Hydro isomerization of linear alkanes to branched isomers is an important petrochemical process for production of gasoline with high octane number.Non-noble metal bifunctional catalysts used in this process always suffer from low metal dispersion and poor metal-acid synergy.Herein,a facile one-pot synthesis method was used to simultaneously regulate metal particle sizes and acidity of the Ni-SAPO-11 hydroisomerization catalyst.The physicochemical properties are investigated using XANES,EXAFS,TEM/STEM,FT-IR,XPS,UV-vis and NH_3-TPD.Apart from the highly dispersed nickel nanoparticles with an average diameter of 8 nm,the framework Ni~(2+)ions are generated via substituting framework Al~(3+)ions of the SAPO-11.The formed NiP-OH structures have lower deprotonation energy(DPE)than the SiAl-OH ones,contributing more and stronger acid sites to the Ni-SAPO-11 catalyst.The great metal-acid synergy including high metal to acid sites ratio(n_(Ni)/n_A)and close intimacy is obtained for the Ni-SAPO-11 catalyst.The Ni-SAPO-11 catalyst outperforms the counterpart prepared by the impregnation method and exhibits comparable activity and isomers selectivity to the Pt/SAPO-11 catalyst in the n-hexane hydroisomerization.展开更多
n-Alkane isomerization is a critical reaction that can affect parameters in oil refining, such as the gasoline octane number and diesel oil solidifying point. In this study, a catalyst support, mordenite (MOR)/silicoa...n-Alkane isomerization is a critical reaction that can affect parameters in oil refining, such as the gasoline octane number and diesel oil solidifying point. In this study, a catalyst support, mordenite (MOR)/silicoaluminophosphate (SAPO)-11 composite zeolite with core/shell structure, was synthesized by hydrothermal method with MOR acting as the seed for crystallization. The crystal structure, elemental composition, surface area, pore volume, and acidity of the catalyst was thoroughly characterized. In addition, the catalytic performance of the as-obtained Pt/MOR/SAPO-11 in the hydroisomerization of n-dodecane was tested. The results indicated that the properties and catalytic performance of the composite molecular sieve were quite different from those of the pure zeolites and physical mixture of MOR and SAPO-11 (MOR+SAPO-11). Compared with the physical mixture, MOR and SAPO-11 were more tightly bound in MOR/SAPO-11 because of chemical bonding. Moreover, the acidity and pore structure were favorable to the catalytic hydroisomerization of n-dodecane. Pt/MOR/SAPO-11 exhibited higher isomerization activity than the Pt-loaded pristine MOR and MOR+SAPO-11. Thus, the core-shell composite molecular sieve has promising industrial applications as the catalyst support.展开更多
Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffracti...Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...展开更多
SAPO-11 molecular sieves were synthesized using silica sol, hydrophilic fumed silica, and tetraethyl orthosilicate（TEOS） as silicon precursors. Their physicochemical properties were characterized using XRD,SEM, nitr...SAPO-11 molecular sieves were synthesized using silica sol, hydrophilic fumed silica, and tetraethyl orthosilicate（TEOS） as silicon precursors. Their physicochemical properties were characterized using XRD,SEM, nitrogen adsorption-desorption, Py-IR, NH;-TPD, EDS, and;Al,;P,;Si MAS NMR techniques. The catalytic performance was assessed in the hydroisomerization of n-octane. The results showed that the silicon precursors influenced the physicochemical properties and catalytic performance of SAPO-11. SAPO-11 synthesized using hydrophilic fumed silica as silicon precursor showed higher silicon distribution and had more medium acid sites. SAPO-11 synthesized using TEOS as silicon precursor had more silicon content, but more silicon islands formed in its framework. The depolymerization of silicon precursors might affect the silicon content and distribution in SAPO-11. In the hydroisomerization of n-octane, the catalytic activity strongly depended on the number of medium acid sites instead of the number of total acid sites.SAPO-11 synthesized using hydrophilic fumed silica as silicon precursor exhibited higher catalytic activity than the other samples because it has more medium acid sites.展开更多
Metal-loaded zeolite catalysts were synthesized and examined in the hydroisomerization of n-decane.Specifically,zeolite Y was impregnated with 0.1 wt%Pd and varying amounts of Ni（0.1-0.5 wt%].The crystallinity of the...Metal-loaded zeolite catalysts were synthesized and examined in the hydroisomerization of n-decane.Specifically,zeolite Y was impregnated with 0.1 wt%Pd and varying amounts of Ni（0.1-0.5 wt%].The crystallinity of the metal-loaded catalysts was characterized by X-ray diffraction,and the average metal particle size was determined by transmission electron microscopy.The states of Pd and Ni were identified by X-ray photoelectron spectroscopy.Ammonia temperature-programmed desorption analysis revealed the occurrence of ion-exchange of some of the catalyst acid sites with Ni-（2＋）.The reducibility of the HY zeolite-supported Pd,Ni,and Pd-Ni catalysts was studied by temperature-programmed reduction.The hydroisomerization of n-decane over the prepared catalyst was conducted at 200-450℃ under 1 atm.Ni addition of up to 0.3 wt%over 0.1 wt%Pd/HY enhanced the n-decane conversion and isomerization product selectivity.The improved selectivity of the mono- and dibranched isomers suggested the occurrence of a protonated cyclopropane intermediate mechanism.However,further Ni addition above 0.3 wt%considerably reduced the activity and isomerization selectivity.The bimetallic catalysts were more selective toward the formation of dibranched isomers,i.e.,those containing a higher octane number.展开更多
ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H;N（CH;）;NH;（HDA）-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powd...ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H;N（CH;）;NH;（HDA）-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powder diffraction（XRD）. The alkaline treated ZSM-48 zeolites maintained its structure under different concentrations of Na OH aqueous solution. Micropores remained unchanged while mesopores with wide pore size distribution formed after the alkaline treatment. The surface area increased from 228 to 288 m;/g. The Br?nsted acid sites had little alteration while an obvious increase of Lewis acid sites was observed. The hydroisomerization of hexadecane was performed as the model reaction to test the effects of the alkali treatment. The conversion of hexadecane had almost no change, which was attributed to the preservation of the Br?nsted acid sites. While high selectivity to iso-hexadecane with an improved iso to normal ratio of alkanes was due to the mesopore formation and improved diffusivity.展开更多
Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen...Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen.Unlike other carbon-based mesoporogens with strong hydrophobicity,the Al_(2)O_(3)/C interacts with phosphoric acid and generates the AlPO_(4)/C structure,which promotes the Al2O3/C dispersion in the synthesis gel of SAPO-11 and avoids the phase separation between them.The Al_(2)O_(3)/C as mesoporogen decreases the crystallite size of SAPO-11 via preventing the aggregation of SAPO-11crystals.Additionally,the addition of Al_(2)O_(3)/C improves the Si distribution in the ACS-11 framework.Consequently,ACS-11 has smaller crystallites,more mesopores,and a greater amount of medium Bronsted acid centers than the conventional microporous SAPO-11 and the SAPO-11 synthesized using activated carbon as mesoporogen.The corresponding Pt/ACS-11 catalyst exhibits the maximal selectivity to multi-branched C10isomers(23.28%) and the minimal cracking selectivity(15.83%) in n-decane hydroisomerization among these catalysts.This research provides a new approach for preparing hierarchical silicoaluminophosphate molecular sieve-based catalysts to produce high-quality fuels.展开更多
The mesoporous materials supported zirconium （Zr-MCM-48） and magnesium （Mg-MCM-48） with three-dimen- sional pore structures and different Zr or Mg contents were prepared via the hydrothermal method, respectively. ...The mesoporous materials supported zirconium （Zr-MCM-48） and magnesium （Mg-MCM-48） with three-dimen- sional pore structures and different Zr or Mg contents were prepared via the hydrothermal method, respectively. The prepared samples were characterized by means of X-ray diffraction （XRD）, scanning electron microscope （SEM）, transmission electron microscope （TEM）, Fourier transform infrared spectroscopy （FT-IR）, NH3 temperature programmed desorption （NH3-TPD） and N2 adsorption-desorption. The XRD, TEM and N2 adsorption-desorption results suggested that M-MCM-48 （where M = Zr, Mg） samples still maintained typical cubic mesoporous framework of MCM-48, with slight decrease of specific surface areas and mesopore orders. The isomerization of n-heptane was carried out as a probe reaction at various factors including the zirconium or magnesium content, reaction time, reaction temperature and weight hourly space veloc- ity （WHSV）. Preliminary results demonstrated that the Mg-MCM-48 catalyst exhibited a higher catalytic activity with a maximum heptane conversion of 91.5% and a corresponding isomerization selectivity of 72.3% as compared to that of Zr- MCM-48. However, for catalytic stability of Mg-MCM-48 for n-heptane isomerization was poorer than Zr-MCM-48, because the Mg-MCM-48 catalyst could maintain a relatively high catalytic activity for only 130 rain, while the Zr-MCM-48 catalyst could maintain a relatively high catalytic activity for more than 190 min without any obvious decrease in performance.展开更多
The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepare...The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepared egg-shell NiPd/CeO_(2)-Al_(2) O_(3) catalyst(NiPdCe) with Pd loading=0.5 wt%,Ni/Pd atomic ratio=1 and CeO_(2) loading=3 wt% was synthesized and characterized,and it was compared with an egg-shell Al_(2) O_(3)-supported Pd based commercial catalyst(PdCC).The reduced catalysts were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy.The textural characteristics and ammonia temperature-programmed desorption profiles of the fresh(unreduced) catalysts were also obtained.Both catalysts show high 1-butyne conversion and selectivity to 1-butene,but the catalysts also present important differences between hydroisomerizing and hydrogenating capabilities.NiPdCe catalyst shows higher capability for hydroisomerization reactions,while the PdCC catalyst exhibits higher hydrogenating capability.The observed catalytic performances can be interesting for some industrial processes and can provide a guideline for the development of a Pd-based catalyst with specific catalytic properties.展开更多
The Ni/SAPO-11 catalyst used for n-hexane hydroisomerization was prepared via a novel two-step crystallization strategy.It involves introduction of nickel salt into the pre-crystalized system of SAPO-11 by grinding fo...The Ni/SAPO-11 catalyst used for n-hexane hydroisomerization was prepared via a novel two-step crystallization strategy.It involves introduction of nickel salt into the pre-crystalized system of SAPO-11 by grinding followed by a second crystallization step.No extra solvent is introduced during the whole synthesis procedure which reduces waste liquid emissions significantly.More importantly,interaction between nickel and support is effectively regulated by the novel method to achieve a well dispersed nickel species and inhibit formation of inert nickel spinel simultaneously.Chemical environments of framework Si are tuned to enhance surface acidity of the Ni/SAPO-11 catalyst.It also shows smaller particle size which favors fast diffusion of reactants and products.Insights into the two-step crystallization indicate that accumulation of SAPO-11 precursors in the pre-crystallization stage,pH regulation by nickel salt and structural directing effect of Ni2+during the second crystallization period account for the rapid crystal growth and smaller particle size of the Ni/SAPO-11 catalyst.All the unique features endow the Ni/SAPO-11 catalyst higher activity and isomers selectivity than the Pt/SAPO-11 catalyst in n-hexane hydroisomerization.展开更多
The effects of adding rare earth(RE) metals,such as Ce,Yb and Pr to Ni-S_2O_8^(2-)/ZrO_2-Al_2O_3(Ni-SZA) on the structure of catalysts as well as their isomerization performance were studied.The prepared catalysts wer...The effects of adding rare earth(RE) metals,such as Ce,Yb and Pr to Ni-S_2O_8^(2-)/ZrO_2-Al_2O_3(Ni-SZA) on the structure of catalysts as well as their isomerization performance were studied.The prepared catalysts were characterized by XRD,BET,FT-IR,Py-IR,and H_2-TPR,The results showed that the addition of RE metals can increase the strength and amounts of the acid sites,improve the redox properties of catalysts.The Yb-Ni-SZA catalyst showed the best redox properties,which could provide enough metallic sites.In addition,it provided the largest amounts of weak and moderately strong acid sites.Among RE metals modified Ni-SZA catalyst,Yb-Ni-SZA exhibited the highest isopentane yield of 61.7%at 160 °C.The optimum isomerization catalytic performance of the catalysts decreased in the order of Yb-Ni-SZA > Pr-Ni-SZA > Ni-SZA > Ce-Ni-SZA.展开更多
基金Project supported by National Natural Science Foundation of China(22078159,U19B2001)。
文摘Hydroisomerization of n-alkanes plays an important role in fuel and lubricants processing.Bifunctional catalysts with ultralow platinum loading have recently been reported successively for hydroisomerisation.Herein,the catalysts were prepared successfully with different methods to improve the catalytic performance.The conversion of 0.01%Pt1@CeOx/SAPO-11 prepared by co-calcination method(0.01%Pt1@CS-c)is 71.4%,25%higher than the other prepared by precipitation method.The turnover frequency per active surface platinum site(TOFPt)of 0.01%Ptl@CS-c is as high as 13115 h^(-1).Revealed by the X-ray photoelectron spectroscopy(XPS)results,the quality of phase boundary/intersurface between ceria and zeolite is found significantly different.The conjunction quality of phase boundary directly affects the spillover rate of intermediate species,which further leads to an apparent activity difference.In addition,the possible role of ceria in the reaction is discussed,rather than just as a carrier for the active metal atoms.
基金the National Natural Science Foundation of China(grant 22208054,22178059 and U23A20113)Natural Science Foundation of Fujian Province,China(grant 2022J01572)+1 种基金Sinochem Quanzhou Energy Technology Co.,Ltd.(grant ZHQZKJ-19-F-ZS-0076)Qingyuan Innovation Laboratory(grant 00121002 and 00523005)for their financial supports.
文摘Hierarchical SAPO-11, featuring both micropore and mesopore channels, demonstrates an outstanding performance in high-octane gasoline production. In this work, we propose an economic and effective approach to directly fabricate hierarchical SAPO-11 molecular sieve from natural kaolin, eliminating the need for mesoporogens. The systematic characterization results show that the kaolin-derived SAPO-11 possesses abundant micro-mesoporous structure and more Brønsted (B) acid sites on the external surface in contrast with the conventional SAPO-11 prepared employing silica sol as silicon source as well as SAPO-11 synthesized with the assist with of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (F127). The analysis of the formation process reveals that the kaolin not only provides silicon source for the SAPO-11 crystal growth, but also offers confined environment for crystal growth along the preferential orientation, resulting in the generation of the microporous and mesoporous structure. Benefiting from these unique properties, the kaolin-derived Pt/SAPO-11 exhibits considerably improved selectivity for di-branched C8 isomers in n-octane hydroisomerization.
基金supported by Graduate Innovation Fund of Heilongjiang Province(YJSCX2012-076HLJ)the Scientific Research Fund of Heilongjiang Provincial Education Department(12521063)
文摘By means of X-ray diffraction（XRD）, N2 adsorption-desorption, Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, NH3-temperature（NH3-TPD）, Py-infrared（Py-IR） and thermogravimetry-differential scanning calorimetry（TG/DTA） techniques, the influences of Ce on the structure, acidity, stability and hydroisomerization performance of Ni-HPW/MCM-48 and Ni-HPW/Ce-MCM-48 catalysts were studied. The results showed that introduction of appropriate content of Ce into MCM-48 could improve the crystallinity, acidity and stability of mesoporous silica. The acidity and stability of the Ni-HPW/Ce-MCM-48 catalyst was also increased. Besides, the catalytic performance of the Ni-HPW/Ce-MCM-48 catalyst for n-heptane hydroisomerization was promoted. The conversion and selectivity of the Ni-HPW/Ce-MCM-48 catalyst reached 41% and 91% respectively at the preparation conditions of 4 wt.% Ni, 20 wt.% HPW, 0.03 Ce/Si molar ratio.
文摘Y-β zeolite composites were hydrotherrnally synthesized by using high silica Y zeolite as the precursor and characterized by XRD, N2 adsorption, SEM and IR spectra of pyridine. The result showed that the N2 adsorption-desorption isotherm of the zeolite composites had a distinct hysteresis loop, and the SEM result showed that the zeolite composites had a different morphology from Y, β and the corresponding physical zeolite mixture. The acid catalytic performance of the zeolite composite catalysts was investigated in the hydrocracking and hydroisomerization of n-octane, and the results showed that the composite materials exhibited an excellent hydrocracking activity and good hydroisomerization performance. The yield of i-C4 over the zeolite composite catalyst was 4.45% higher than that on the corresponding zeolite mixture in the n-octane hydrocracking process at 553 K. The isomerization ability of n-octane over the composite catalyst was 3.6 fold that of the corresponding mixture at 503 K.
文摘Zinc-modified Pt/SAPO-11 catalysts were prepared by incipient wetness impregnation and assessed in the hydroisomerization of n-octane.Their physicochemical properties were investigated using powder X-ray diffraction,scanning electron microscopy,nitrogen adsorption-desorption,pyridine-adsorbed infrared spectroscopy,temperature-programmed desorption of NH3,temperature-programmed reduction of hydrogen,temperature-programmed desorption of hydrogen,transmission electron microscopy,and X-ray photoelectron spectroscopy.The addition of zinc resulted in high dispersion of platinum.Zinc acted as a competitive adsorbent,changed the location of platinum.The catalyst with a zinc loading of 0.5%gave the highest selectivity to dimethylhexanes,but the conversion was lower than those achieved with the other catalysts.Dimethylhexanes have large molecular diameters,and therefore their diffusion may be difficult.This weakens the catalytic activity of the zinc-modified catalysts and lowers the n-octane conversion.
基金supported by the National Natural Science Foundation of China(21776295)the Youth Innovation Promotion Association,CAS(2017355)~~
文摘A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,the performance of the obtained bifunctional catalysts toward the hydroisomerization of n-dodecane was examined.The prepared samples were characterized by XRD,SEM,BET,XRF,Py-IR,and solid-state NMR.From the results,it was found that the high crystallinity and uniform morphology were retained after the post-treatment and that more(002)crystal faces were exposed,which was beneficial since more acid sites were provided.More importantly,the total Bronsted acid sites and the ratio(Ra)of the micropore area to the total surface area were optimized by this method.Thus,the catalytic performance was enhanced significantly,and the prepared Pt-SAPO-11-10%catalyst had the highest i-dodecane yield of 80.1%compared to 55.3%of Pt-SAPO-11.Expectedly,this facile and cost-effective method is promising for the hydroisomerization of normal paraffin in the production of lubricant base oils.
基金Supported by the Jiangsu Provincial Key Natural Science Foundation for Universities（06KJA53012） the National Natural Science Foundation of China（20476046 20976084）
文摘A series of Pt catalysts supported on the Hβ-zeolite that is ion-exchanged with the rare earth metal ions of Ce（III） and La（III）,are prepared by impregnation,characterized by inductively coupled plasma （ICP）,X-ray diffraction （XRD）,BET,temperature-programmed desorption of ammonia （NH3-TPD）,temperature-programmed reduction of hydrogen （H2-TPR） and H2-chemisorption techniques,and evaluated in the hydroisomerization of n-heptane with an atmospheric fixed-bed reactor.The reaction temperature,time on stream,space velocity,and the ratio of H2/n-heptane are changed to get the optimal conditions.The Ce（III） and La（III）-exchanged Hβ-zeolites exhibit higher selectivity for isomerized products than the neat Hβ-zeolite.Moreover,the Ce（III）-exchanged catalysts give higher conversions of n-heptane,whereas the La（III）-exchanged ones do not show any improvement in con-version.Under optimal conditions,the catalyst with 0.4% （by mass） Pt and 0.5% （by mass） Ce loading presents very high selectivity of isomerized products of 95.1% coupled with high n-heptane conversion of 68.7%.Effects of the ion-exchange of Ce（III） and La（III） on the catalytic performance are discussed in relation with the physico-chemical properties of catalysts.
基金supported by the National Natural Science Foundation of China (No. 21676300)
文摘The bimetallic NiCu/SAPO-11 catalysts were prepared by co-impregnation, sequential impregnation, coprecipitation, and mechanical mixing methods. Powder X-ray diffraction, nitrogen adsorption-desorption,temperature-programmed desorption of ammonia, transmission electron microscopy, temperatureprogrammed reduction of hydrogen, and X-ray photoelectron spectroscopy were used to characterize the physicochemical properties of the catalysts. The catalytic performance of the catalysts was assessed by the hydroisomerization of n-octane. Results indicated that the conversion of n-octane and selectivity to n-octane isomers were related to the preparation methods of the catalysts. The catalysts with Ni-Cu alloy effectively restrained the hydrogenolysis reaction that decreases the selectivity of isomerization. The catalyst prepared by the mechanical mixing of NiO and CuO hardly formed Ni-Cu alloy, showing obvious hydrogenolysis and low selectivity to n-octane isomers. The unbalance between the metal and acid sites resulted in the low conversion of n-octane and selectivity to n-octane isomers. Among all the catalysts,the catalyst prepared by the co-impregnation method exhibited high catalytic activity and selectivity to n-octane isomers.
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 ℃.
基金the National Natural Science Foundation of China(21978326 and 21991091)the Fundamental Research Funds for the Central Universities(20CX06059A)+2 种基金the China Postdoctoral Science Foundation(2020M682259)the Postdoctoral Applied Research Project of Qingdao(qd20200002)the Natural Science Foundation of Shandong Province(ZR2019MB029)。
文摘Hydro isomerization of linear alkanes to branched isomers is an important petrochemical process for production of gasoline with high octane number.Non-noble metal bifunctional catalysts used in this process always suffer from low metal dispersion and poor metal-acid synergy.Herein,a facile one-pot synthesis method was used to simultaneously regulate metal particle sizes and acidity of the Ni-SAPO-11 hydroisomerization catalyst.The physicochemical properties are investigated using XANES,EXAFS,TEM/STEM,FT-IR,XPS,UV-vis and NH_3-TPD.Apart from the highly dispersed nickel nanoparticles with an average diameter of 8 nm,the framework Ni~(2+)ions are generated via substituting framework Al~(3+)ions of the SAPO-11.The formed NiP-OH structures have lower deprotonation energy(DPE)than the SiAl-OH ones,contributing more and stronger acid sites to the Ni-SAPO-11 catalyst.The great metal-acid synergy including high metal to acid sites ratio(n_(Ni)/n_A)and close intimacy is obtained for the Ni-SAPO-11 catalyst.The Ni-SAPO-11 catalyst outperforms the counterpart prepared by the impregnation method and exhibits comparable activity and isomers selectivity to the Pt/SAPO-11 catalyst in the n-hexane hydroisomerization.
基金the National Natural Science Fund of China (2016-Z0030)the Natural Science Foundation of Liaoning Province (L2017LQN008, L2016020)the Fushun Science & Technology Program (2011ZX05039-003)
文摘n-Alkane isomerization is a critical reaction that can affect parameters in oil refining, such as the gasoline octane number and diesel oil solidifying point. In this study, a catalyst support, mordenite (MOR)/silicoaluminophosphate (SAPO)-11 composite zeolite with core/shell structure, was synthesized by hydrothermal method with MOR acting as the seed for crystallization. The crystal structure, elemental composition, surface area, pore volume, and acidity of the catalyst was thoroughly characterized. In addition, the catalytic performance of the as-obtained Pt/MOR/SAPO-11 in the hydroisomerization of n-dodecane was tested. The results indicated that the properties and catalytic performance of the composite molecular sieve were quite different from those of the pure zeolites and physical mixture of MOR and SAPO-11 (MOR+SAPO-11). Compared with the physical mixture, MOR and SAPO-11 were more tightly bound in MOR/SAPO-11 because of chemical bonding. Moreover, the acidity and pore structure were favorable to the catalytic hydroisomerization of n-dodecane. Pt/MOR/SAPO-11 exhibited higher isomerization activity than the Pt-loaded pristine MOR and MOR+SAPO-11. Thus, the core-shell composite molecular sieve has promising industrial applications as the catalyst support.
基金supported by the Foundation of Jiangsu Key Laboratory of Precious Metals Chemistry (SYGK0710)Natural Scientific Foundation of Jiangsu Teachers University of Technology (KYY06029)
文摘Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...
基金supported by the National Natural Science Foundation,China(no.21676300)
文摘SAPO-11 molecular sieves were synthesized using silica sol, hydrophilic fumed silica, and tetraethyl orthosilicate（TEOS） as silicon precursors. Their physicochemical properties were characterized using XRD,SEM, nitrogen adsorption-desorption, Py-IR, NH;-TPD, EDS, and;Al,;P,;Si MAS NMR techniques. The catalytic performance was assessed in the hydroisomerization of n-octane. The results showed that the silicon precursors influenced the physicochemical properties and catalytic performance of SAPO-11. SAPO-11 synthesized using hydrophilic fumed silica as silicon precursor showed higher silicon distribution and had more medium acid sites. SAPO-11 synthesized using TEOS as silicon precursor had more silicon content, but more silicon islands formed in its framework. The depolymerization of silicon precursors might affect the silicon content and distribution in SAPO-11. In the hydroisomerization of n-octane, the catalytic activity strongly depended on the number of medium acid sites instead of the number of total acid sites.SAPO-11 synthesized using hydrophilic fumed silica as silicon precursor exhibited higher catalytic activity than the other samples because it has more medium acid sites.
文摘Metal-loaded zeolite catalysts were synthesized and examined in the hydroisomerization of n-decane.Specifically,zeolite Y was impregnated with 0.1 wt%Pd and varying amounts of Ni（0.1-0.5 wt%].The crystallinity of the metal-loaded catalysts was characterized by X-ray diffraction,and the average metal particle size was determined by transmission electron microscopy.The states of Pd and Ni were identified by X-ray photoelectron spectroscopy.Ammonia temperature-programmed desorption analysis revealed the occurrence of ion-exchange of some of the catalyst acid sites with Ni-（2＋）.The reducibility of the HY zeolite-supported Pd,Ni,and Pd-Ni catalysts was studied by temperature-programmed reduction.The hydroisomerization of n-decane over the prepared catalyst was conducted at 200-450℃ under 1 atm.Ni addition of up to 0.3 wt%over 0.1 wt%Pd/HY enhanced the n-decane conversion and isomerization product selectivity.The improved selectivity of the mono- and dibranched isomers suggested the occurrence of a protonated cyclopropane intermediate mechanism.However,further Ni addition above 0.3 wt%considerably reduced the activity and isomerization selectivity.The bimetallic catalysts were more selective toward the formation of dibranched isomers,i.e.,those containing a higher octane number.
基金supported by the National Natural Science Foundation of China(21073023)
文摘ZSM-48 zeolites with various Si/Al ratios were hydrothermally synthesized in the H;N（CH;）;NH;（HDA）-containing media. The obtained samples were highly crystallized with minor mixed phases as evidenced by X-ray powder diffraction（XRD）. The alkaline treated ZSM-48 zeolites maintained its structure under different concentrations of Na OH aqueous solution. Micropores remained unchanged while mesopores with wide pore size distribution formed after the alkaline treatment. The surface area increased from 228 to 288 m;/g. The Br?nsted acid sites had little alteration while an obvious increase of Lewis acid sites was observed. The hydroisomerization of hexadecane was performed as the model reaction to test the effects of the alkali treatment. The conversion of hexadecane had almost no change, which was attributed to the preservation of the Br?nsted acid sites. While high selectivity to iso-hexadecane with an improved iso to normal ratio of alkanes was due to the mesopore formation and improved diffusivity.
基金financial support of Science Foundation of China University of Petroleum,Beijing(Grant No.KYJJ2012-03-03)
文摘Hierarchical SAPO-11 molecular sieve(ACS-11) was successfully synthesized employing the Al2O3/carbon(Al_(2)O_(3)/C) composite obtained through the pyrolysis of Al-based metal-organic framework(Al-MOF-96)as mesoporogen.Unlike other carbon-based mesoporogens with strong hydrophobicity,the Al_(2)O_(3)/C interacts with phosphoric acid and generates the AlPO_(4)/C structure,which promotes the Al2O3/C dispersion in the synthesis gel of SAPO-11 and avoids the phase separation between them.The Al_(2)O_(3)/C as mesoporogen decreases the crystallite size of SAPO-11 via preventing the aggregation of SAPO-11crystals.Additionally,the addition of Al_(2)O_(3)/C improves the Si distribution in the ACS-11 framework.Consequently,ACS-11 has smaller crystallites,more mesopores,and a greater amount of medium Bronsted acid centers than the conventional microporous SAPO-11 and the SAPO-11 synthesized using activated carbon as mesoporogen.The corresponding Pt/ACS-11 catalyst exhibits the maximal selectivity to multi-branched C10isomers(23.28%) and the minimal cracking selectivity(15.83%) in n-decane hydroisomerization among these catalysts.This research provides a new approach for preparing hierarchical silicoaluminophosphate molecular sieve-based catalysts to produce high-quality fuels.
基金supported by the postdoctoral programme for chemical engineering and technology of Northeast Petroleum Universitythe Youth Fund of Northeast Petroleum University(grant number NEPUQN2015-1-08)+2 种基金the Cultivation Fund of Northeast Petroleum University [grant number 2017PYYL-03]the Daqing Science and Technology Plan Projects [grant number szdfy-2015-04]the College Students’ Innovative Entrepreneurial Training Plan Projects of Heilongjiang Province [grant number 201710220030]
文摘The mesoporous materials supported zirconium （Zr-MCM-48） and magnesium （Mg-MCM-48） with three-dimen- sional pore structures and different Zr or Mg contents were prepared via the hydrothermal method, respectively. The prepared samples were characterized by means of X-ray diffraction （XRD）, scanning electron microscope （SEM）, transmission electron microscope （TEM）, Fourier transform infrared spectroscopy （FT-IR）, NH3 temperature programmed desorption （NH3-TPD） and N2 adsorption-desorption. The XRD, TEM and N2 adsorption-desorption results suggested that M-MCM-48 （where M = Zr, Mg） samples still maintained typical cubic mesoporous framework of MCM-48, with slight decrease of specific surface areas and mesopore orders. The isomerization of n-heptane was carried out as a probe reaction at various factors including the zirconium or magnesium content, reaction time, reaction temperature and weight hourly space veloc- ity （WHSV）. Preliminary results demonstrated that the Mg-MCM-48 catalyst exhibited a higher catalytic activity with a maximum heptane conversion of 91.5% and a corresponding isomerization selectivity of 72.3% as compared to that of Zr- MCM-48. However, for catalytic stability of Mg-MCM-48 for n-heptane isomerization was poorer than Zr-MCM-48, because the Mg-MCM-48 catalyst could maintain a relatively high catalytic activity for only 130 rain, while the Zr-MCM-48 catalyst could maintain a relatively high catalytic activity for more than 190 min without any obvious decrease in performance.
基金Project supported by the Fondo Nacional de Ciencia,Tecnología e Innovación(FONACIT-G-2005000437)Universidad Nacional de La Plata(UNLP-PID1226)+1 种基金Consejo Nacional de Investigaciones Científicas y Técnicas(CONICET-PIP0018)Agenda Nacional de Promoción Cientifica y Tecnológica(ANPCyT-PICT 2015/3546)。
文摘The catalytic performance during the 1-butyne hydrogenation using two reduced Al_(2) O_(3)-supported Pdbased catalysts was carried out in a total recirculation system with an external fixed-bed reactor.The lab-prepared egg-shell NiPd/CeO_(2)-Al_(2) O_(3) catalyst(NiPdCe) with Pd loading=0.5 wt%,Ni/Pd atomic ratio=1 and CeO_(2) loading=3 wt% was synthesized and characterized,and it was compared with an egg-shell Al_(2) O_(3)-supported Pd based commercial catalyst(PdCC).The reduced catalysts were characterized by X-ray diffraction,X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy.The textural characteristics and ammonia temperature-programmed desorption profiles of the fresh(unreduced) catalysts were also obtained.Both catalysts show high 1-butyne conversion and selectivity to 1-butene,but the catalysts also present important differences between hydroisomerizing and hydrogenating capabilities.NiPdCe catalyst shows higher capability for hydroisomerization reactions,while the PdCC catalyst exhibits higher hydrogenating capability.The observed catalytic performances can be interesting for some industrial processes and can provide a guideline for the development of a Pd-based catalyst with specific catalytic properties.
基金supported by the National Natural Science Foundation of China(22108308,21978326,21991091)the Natural Science Foundation of Shandong Province(ZR2021QB062,ZR2019MB029)+2 种基金the China Postdoctoral Science Foundation(2020M682259)the Project of Qingdao West Coast New Area District Science and Technology Innovation Center(Grant No.20202-2)the Fundamental Research Funds for the Central Universities(22CX06014A)。
文摘The Ni/SAPO-11 catalyst used for n-hexane hydroisomerization was prepared via a novel two-step crystallization strategy.It involves introduction of nickel salt into the pre-crystalized system of SAPO-11 by grinding followed by a second crystallization step.No extra solvent is introduced during the whole synthesis procedure which reduces waste liquid emissions significantly.More importantly,interaction between nickel and support is effectively regulated by the novel method to achieve a well dispersed nickel species and inhibit formation of inert nickel spinel simultaneously.Chemical environments of framework Si are tuned to enhance surface acidity of the Ni/SAPO-11 catalyst.It also shows smaller particle size which favors fast diffusion of reactants and products.Insights into the two-step crystallization indicate that accumulation of SAPO-11 precursors in the pre-crystallization stage,pH regulation by nickel salt and structural directing effect of Ni2+during the second crystallization period account for the rapid crystal growth and smaller particle size of the Ni/SAPO-11 catalyst.All the unique features endow the Ni/SAPO-11 catalyst higher activity and isomers selectivity than the Pt/SAPO-11 catalyst in n-hexane hydroisomerization.
基金Supported by the Technology Risk Innovation Foundation of China National Petroleum Corporation(07-06D-01-04-03-02)
文摘The effects of adding rare earth(RE) metals,such as Ce,Yb and Pr to Ni-S_2O_8^(2-)/ZrO_2-Al_2O_3(Ni-SZA) on the structure of catalysts as well as their isomerization performance were studied.The prepared catalysts were characterized by XRD,BET,FT-IR,Py-IR,and H_2-TPR,The results showed that the addition of RE metals can increase the strength and amounts of the acid sites,improve the redox properties of catalysts.The Yb-Ni-SZA catalyst showed the best redox properties,which could provide enough metallic sites.In addition,it provided the largest amounts of weak and moderately strong acid sites.Among RE metals modified Ni-SZA catalyst,Yb-Ni-SZA exhibited the highest isopentane yield of 61.7%at 160 °C.The optimum isomerization catalytic performance of the catalysts decreased in the order of Yb-Ni-SZA > Pr-Ni-SZA > Ni-SZA > Ce-Ni-SZA.
