The thermal decomposition of n-heptane is an important process in petroleum industry. The theoretical investigations show that the main products are C2H4, H2, CH4, and C3H6, which agree well with the experimental resu...The thermal decomposition of n-heptane is an important process in petroleum industry. The theoretical investigations show that the main products are C2H4, H2, CH4, and C3H6, which agree well with the experimental results. The products populations depend strongly on the temperature. The quantity of ethylene increases quickly as the temperature goes up. The conversion of n-heptane and the mole fraction of primary products from reactive molecular dynamic and chemical kinetic modeling are compared with each other. We also investigated the pre-exponential factor and activation energy for thermal decomposition of n-heptane by kinetic analysis from the reactive force field simulations, which were extracted to be 1.78×10^14 s^-1 and 47.32 kcal/mol respectively.展开更多
n-Heptane is the most important straight chain paramn in the fossil-fuel industry. In this work, pyrolysis behavior of n-heptane at high temperature is investigated by a se- ties of ReaxFF based reactive molecular dyn...n-Heptane is the most important straight chain paramn in the fossil-fuel industry. In this work, pyrolysis behavior of n-heptane at high temperature is investigated by a se- ties of ReaxFF based reactive molecular dynamics simulations. Temperature effects on the n-heptane pyrolysis and related products distributions have been detailedly analyzed. The simulation results indicate that the temperature effect is characterized in stages. High tern- perature can accelerate the decomposition of n-heptane, but the influence becomes small after it reaches a certain level. According to the different reaction behaviors, pyrolysis of n-heptane could be divided into three stages. The variation trends of the mass fraction evolu- tion of ethylene （C2H4）, C3, and C4 calculated from reactive molecular dynamics simulations are in good agreement with the previous experimental results. The apparent activation en- ergy extracted from the first-order kinetic analysis is 53.96 kcal/mol and a pre-exponential factor is 55.34×10^13 s-1, which is reasonably consistent with the experimental results.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
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
Pt-（Sn,Re）/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200–350 ℃.To characterize the catalyst,X-ray diffraction,X-ray fluorescene,Fourier transform infrared spectroscopy,ultraviolet-visible d...Pt-（Sn,Re）/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200–350 ℃.To characterize the catalyst,X-ray diffraction,X-ray fluorescene,Fourier transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,temperature-programmed reduction of H2,temperature-programmed desorption of NH3,infrared spectroscopy of adsorbed pyridine,H2 chemisorption,nitrogen adsorption-desorption,scanning electron microscopy and thermogravimetric analysis were performed.Kinetics of n-C7 isomerization were investigated under various hydrogen and n-C7 pressures,and the effects of reaction conditions on catalytic performance were studied.The results showed that bi-and trimetallic catalysts exhibit better performance than monometallic catalysts for this reaction.For example,a maximum i-C7 selectivity（ 〉74%） and multibranched isomer selectivity（40%） were observed for Pt-Sn/HZSM5-HMS at 200 ℃.展开更多
The SiO2 and g-Al2O3 supported MoOx catalyst and a MoOx-SiO2 catalyst have been studied in a conventional fixed-bed flow reactor for n-alkanes isomerization. It is shown that the MoOx-SiO2 catalyst with SiO2 framewor...The SiO2 and g-Al2O3 supported MoOx catalyst and a MoOx-SiO2 catalyst have been studied in a conventional fixed-bed flow reactor for n-alkanes isomerization. It is shown that the MoOx-SiO2 catalyst with SiO2 framework, in which the bulk MoOx phase is large enough to form typical mesoporous structure, is promising in terms of its advantages of both improved mechanical strength and high catalytic properties over the supported MoOx and bulk MoOx catalyst.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
Single-crystalline hierarchical ZSM-5 zeolites with different particle sizes(namely 100,140,and 200 nm)were successfully prepared by adjusting the amount of tetrapropylammonium hydroxide(TPAOH),and investigated in n-h...Single-crystalline hierarchical ZSM-5 zeolites with different particle sizes(namely 100,140,and 200 nm)were successfully prepared by adjusting the amount of tetrapropylammonium hydroxide(TPAOH),and investigated in n-heptane catalytic cracking reaction.Diffusional measurements by zero-length column(ZLC)method showed that the apparent diffusivities of n-heptane decreased with the reduction of particle size,indicating the existence of surface barriers.Moreover,with the decrease of particle size,the additional diffusion path length increased,which meant the influence of surface barriers became more apparent.Despite the change of surface barriers,the intracrystalline diffusion still dominated the overall diffusion.Catalytic performance showed that the zeolite with smaller particle size had better stability.展开更多
Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation...Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.展开更多
The 0.4%Pt/xSTA-MIL-101(Cr)metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr)as the support.The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101...The 0.4%Pt/xSTA-MIL-101(Cr)metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr)as the support.The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101(Cr)and the pore structure was arranged orderly.The specific surface area of the samples was extremely high and the samples were made of micro-mesoporous composite materials.Silicotungstic acid could retain its Keggin structure in the 0.4%Pt/xSTA-MIL-101(Cr)samples and the catalyst possessed moderately strong Brønsted acid sites.Besides,the dispersion of Pt particles in MIL-101(Cr)was relatively high.n-Heptane isomerization was first used as a probe to test the novel 0.4%Pt/xSTA-MIL-10(Cr)catalyst.Compared with the conventional silicate catalysts,the catalytic performance of 0.4%Pt/30%STA-MIL-101(Cr)was significantly improved with a n-heptane conversion of 58.93%and an iso-heptane selectivity of 95.68%,respectively,under conditions covering a reaction time of 2 h and a reaction temperature of 260°C.The catalyst could still maintain a relatively high catalytic performance after a reaction time of 5 h.Compared with the non-noble metal catalyst,the catalytic efficiency of 0.4%Pt/30%STA-MIL-101(Cr)is relatively high.The mechanism model of n-heptane isomerization over 0.4%Pt/xSTA-MIL-101(Cr)catalyst was established.展开更多
The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence ...The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas. XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5, leading to more ordered framework structure and larger surface area. TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5. Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Bro¨nsted and Lewis acid sites without changing the lattice structure of HZSM-5. The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%, 33.2% and 11.8% in conversion, selectivity and yield of n-heptane isomerization, respectively.展开更多
Supported NiCu bimetallic catalysts have been produced in-situ on commercial Al_(2)O_(3)by using layered double hydroxides as precursors.The resulting catalysts show a uniform Ni and Cu distribution,thus providing goo...Supported NiCu bimetallic catalysts have been produced in-situ on commercial Al_(2)O_(3)by using layered double hydroxides as precursors.The resulting catalysts show a uniform Ni and Cu distribution,thus providing good activity and selectivity in the reforming reaction of n-heptane.The catalytic performance has been found to depend on the Cu/Ni ratio,revealing the synergic catalysis between homogeneously dispersed Ni and Cu sites.The good catalysis of Ni Cu bimetallic catalysts makes it possible to partly or even completely replace Pt with NiCu bimetallic catalysts.展开更多
Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoroprop...Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoropropane（BDAF） by the two-step polymerization method. The polymer was proved to be polyimide 6FDA-BDAF by the Fourier transform infrared（FT-IR）, the 1H-NMR and ^（19）F-NMR spectra. An asymmetric membrane was prepared with the synthesized polyimide 6FDA-BDAF, it was porous in the 50 μm height bulk and dense in a 3–5 μm height surface. The membrane was used to separate n-heptane/thiophene mixtures by pervaporation with sulfur（S） contents from 50 to 900 μg g^（–1）. The total flux was enlarged from 7.96 to 37.61 kg m^（–2） h^（–1） with temperature increasing from 50 to 90°C. The membrane＇s enrichments factor for thiophene were about 3.13 and dependent on the experimental conditions. The experimental results demonstrated that polyimide 6FDA-BDAF would be a potential membrane material for desulfurization and controlled release of the S-containing fertilizer.展开更多
Solubilities of CO<sub>2</sub> in binary mixtures of n-decane-n-hexadecane and n-heptane-toluenewere measured in a glass apparatus by a synthetic method.Henry’s constants at several temperaturesand solven...Solubilities of CO<sub>2</sub> in binary mixtures of n-decane-n-hexadecane and n-heptane-toluenewere measured in a glass apparatus by a synthetic method.Henry’s constants at several temperaturesand solvent compositions were reported.While the Henry’s constants of CO<sub>2</sub> in mixtures of decaneand hexadecane can be satisfactorily predicted by a simple linear interpolation,prediction of Henry’sconstants for CO<sub>2</sub> in mixtures of heptane and toluene requires excess Gibbs energy of the solvent mix-tures.The standard thermodynamic functions of solution（ΔH<sup>0</sup>,ΔG<sup>0</sup>,and ΔS<sup>0</sup>）were reported.展开更多
The present paper reports new results regarding the addition of pseudo-boehmite as a binder during the synthesis of shaped Pt/WO_(3)-ZrO_(2)-Al_(2)O_(3) (PtWZA) catalysts. Binder shaping can noticeably influence not o...The present paper reports new results regarding the addition of pseudo-boehmite as a binder during the synthesis of shaped Pt/WO_(3)-ZrO_(2)-Al_(2)O_(3) (PtWZA) catalysts. Binder shaping can noticeably influence not only the structure and acidity of catalyst and improve its catalytic performance with regard to n-heptane isomerization, but the mechanical strength of the catalyst. A suitable binder content can improve the isomerization activity or selectivity by changing the acidity of PtWZA. The influence of the binder content depends on the WO_(3) content of the catalyst. PtWZA catalysts that contain 5%-15% binder on a dry basis exhibit favorable isomerization performance that depends on WO_(3) content. Suitable catalysts include Pt20WZ5A and Pt30WZ15A, which provide conversions of approximately 80%-90% and a selectivity of 90%. These new findings enrich researcher knowledge of the effect of the binder on the catalyst shaping process and are useful in the production of industrial catalysts.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21103117）.
文摘The thermal decomposition of n-heptane is an important process in petroleum industry. The theoretical investigations show that the main products are C2H4, H2, CH4, and C3H6, which agree well with the experimental results. The products populations depend strongly on the temperature. The quantity of ethylene increases quickly as the temperature goes up. The conversion of n-heptane and the mole fraction of primary products from reactive molecular dynamic and chemical kinetic modeling are compared with each other. We also investigated the pre-exponential factor and activation energy for thermal decomposition of n-heptane by kinetic analysis from the reactive force field simulations, which were extracted to be 1.78×10^14 s^-1 and 47.32 kcal/mol respectively.
基金This work was supported by the National Natural Science Foundation of China （No.20273066）.
文摘n-Heptane is the most important straight chain paramn in the fossil-fuel industry. In this work, pyrolysis behavior of n-heptane at high temperature is investigated by a se- ties of ReaxFF based reactive molecular dynamics simulations. Temperature effects on the n-heptane pyrolysis and related products distributions have been detailedly analyzed. The simulation results indicate that the temperature effect is characterized in stages. High tern- perature can accelerate the decomposition of n-heptane, but the influence becomes small after it reaches a certain level. According to the different reaction behaviors, pyrolysis of n-heptane could be divided into three stages. The variation trends of the mass fraction evolu- tion of ethylene （C2H4）, C3, and C4 calculated from reactive molecular dynamics simulations are in good agreement with the previous experimental results. The apparent activation en- ergy extracted from the first-order kinetic analysis is 53.96 kcal/mol and a pre-exponential factor is 55.34×10^13 s-1, which is reasonably consistent with the experimental results.
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.
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.
文摘Pt-（Sn,Re）/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200–350 ℃.To characterize the catalyst,X-ray diffraction,X-ray fluorescene,Fourier transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,temperature-programmed reduction of H2,temperature-programmed desorption of NH3,infrared spectroscopy of adsorbed pyridine,H2 chemisorption,nitrogen adsorption-desorption,scanning electron microscopy and thermogravimetric analysis were performed.Kinetics of n-C7 isomerization were investigated under various hydrogen and n-C7 pressures,and the effects of reaction conditions on catalytic performance were studied.The results showed that bi-and trimetallic catalysts exhibit better performance than monometallic catalysts for this reaction.For example,a maximum i-C7 selectivity（ 〉74%） and multibranched isomer selectivity（40%） were observed for Pt-Sn/HZSM5-HMS at 200 ℃.
文摘The SiO2 and g-Al2O3 supported MoOx catalyst and a MoOx-SiO2 catalyst have been studied in a conventional fixed-bed flow reactor for n-alkanes isomerization. It is shown that the MoOx-SiO2 catalyst with SiO2 framework, in which the bulk MoOx phase is large enough to form typical mesoporous structure, is promising in terms of its advantages of both improved mechanical strength and high catalytic properties over the supported MoOx and bulk MoOx catalyst.
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The support from the National Natural Science Foundation of China(22278353)is greatly appreciated。
文摘Single-crystalline hierarchical ZSM-5 zeolites with different particle sizes(namely 100,140,and 200 nm)were successfully prepared by adjusting the amount of tetrapropylammonium hydroxide(TPAOH),and investigated in n-heptane catalytic cracking reaction.Diffusional measurements by zero-length column(ZLC)method showed that the apparent diffusivities of n-heptane decreased with the reduction of particle size,indicating the existence of surface barriers.Moreover,with the decrease of particle size,the additional diffusion path length increased,which meant the influence of surface barriers became more apparent.Despite the change of surface barriers,the intracrystalline diffusion still dominated the overall diffusion.Catalytic performance showed that the zeolite with smaller particle size had better stability.
基金the financial support from the National Natural Science Foundation of China (21908010)the Education Department of Jilin Province (JJKH20220694KJ)。
文摘Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.
文摘The 0.4%Pt/xSTA-MIL-101(Cr)metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr)as the support.The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101(Cr)and the pore structure was arranged orderly.The specific surface area of the samples was extremely high and the samples were made of micro-mesoporous composite materials.Silicotungstic acid could retain its Keggin structure in the 0.4%Pt/xSTA-MIL-101(Cr)samples and the catalyst possessed moderately strong Brønsted acid sites.Besides,the dispersion of Pt particles in MIL-101(Cr)was relatively high.n-Heptane isomerization was first used as a probe to test the novel 0.4%Pt/xSTA-MIL-10(Cr)catalyst.Compared with the conventional silicate catalysts,the catalytic performance of 0.4%Pt/30%STA-MIL-101(Cr)was significantly improved with a n-heptane conversion of 58.93%and an iso-heptane selectivity of 95.68%,respectively,under conditions covering a reaction time of 2 h and a reaction temperature of 260°C.The catalyst could still maintain a relatively high catalytic performance after a reaction time of 5 h.Compared with the non-noble metal catalyst,the catalytic efficiency of 0.4%Pt/30%STA-MIL-101(Cr)is relatively high.The mechanism model of n-heptane isomerization over 0.4%Pt/xSTA-MIL-101(Cr)catalyst was established.
基金supported by the Ministry of Science,Technology and Innovation,Malaysia through E-Science Fund Research Project(No.03-01-06-SF0564 and 03-01-06-SF0289)the Hitachi Scholarship Foundation for the Gas Chromatograph Instrument Grant
文摘The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas. XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5, leading to more ordered framework structure and larger surface area. TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5. Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Bro¨nsted and Lewis acid sites without changing the lattice structure of HZSM-5. The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%, 33.2% and 11.8% in conversion, selectivity and yield of n-heptane isomerization, respectively.
基金Financial supports from National Nature Science Foundation of China(NSFC,Nos.91634120 and 21521005)the National Key Research and Development Program of China(No.2017YFA0206804)the Fundamental Research Funds for the Central Universities(No.XK1802-6)。
文摘Supported NiCu bimetallic catalysts have been produced in-situ on commercial Al_(2)O_(3)by using layered double hydroxides as precursors.The resulting catalysts show a uniform Ni and Cu distribution,thus providing good activity and selectivity in the reforming reaction of n-heptane.The catalytic performance has been found to depend on the Cu/Ni ratio,revealing the synergic catalysis between homogeneously dispersed Ni and Cu sites.The good catalysis of Ni Cu bimetallic catalysts makes it possible to partly or even completely replace Pt with NiCu bimetallic catalysts.
基金support from the Key Technology R&D Program of China(2011BAD11B05)the National Nonprofit Institute Research Grant of Chinese Academy of Agricultural Sciences(2011-28,2013-17)+3 种基金supported by the National Basic Research Program of China(973 Program,2003CB615701)the National Natural Science Foundation of China(20576059,20676067,31572204)the China Petroleum&Chemical Corporation(SINOPEC Foundation,X505002)the China National Petroleum Corporation(CNPC)InnovationFoundation(05051143)
文摘Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoropropane（BDAF） by the two-step polymerization method. The polymer was proved to be polyimide 6FDA-BDAF by the Fourier transform infrared（FT-IR）, the 1H-NMR and ^（19）F-NMR spectra. An asymmetric membrane was prepared with the synthesized polyimide 6FDA-BDAF, it was porous in the 50 μm height bulk and dense in a 3–5 μm height surface. The membrane was used to separate n-heptane/thiophene mixtures by pervaporation with sulfur（S） contents from 50 to 900 μg g^（–1）. The total flux was enlarged from 7.96 to 37.61 kg m^（–2） h^（–1） with temperature increasing from 50 to 90°C. The membrane＇s enrichments factor for thiophene were about 3.13 and dependent on the experimental conditions. The experimental results demonstrated that polyimide 6FDA-BDAF would be a potential membrane material for desulfurization and controlled release of the S-containing fertilizer.
文摘Solubilities of CO<sub>2</sub> in binary mixtures of n-decane-n-hexadecane and n-heptane-toluenewere measured in a glass apparatus by a synthetic method.Henry’s constants at several temperaturesand solvent compositions were reported.While the Henry’s constants of CO<sub>2</sub> in mixtures of decaneand hexadecane can be satisfactorily predicted by a simple linear interpolation,prediction of Henry’sconstants for CO<sub>2</sub> in mixtures of heptane and toluene requires excess Gibbs energy of the solvent mix-tures.The standard thermodynamic functions of solution（ΔH<sup>0</sup>,ΔG<sup>0</sup>,and ΔS<sup>0</sup>）were reported.
基金financial support from the National Natural Science Foundation of P. R. China (21103049)
文摘The present paper reports new results regarding the addition of pseudo-boehmite as a binder during the synthesis of shaped Pt/WO_(3)-ZrO_(2)-Al_(2)O_(3) (PtWZA) catalysts. Binder shaping can noticeably influence not only the structure and acidity of catalyst and improve its catalytic performance with regard to n-heptane isomerization, but the mechanical strength of the catalyst. A suitable binder content can improve the isomerization activity or selectivity by changing the acidity of PtWZA. The influence of the binder content depends on the WO_(3) content of the catalyst. PtWZA catalysts that contain 5%-15% binder on a dry basis exhibit favorable isomerization performance that depends on WO_(3) content. Suitable catalysts include Pt20WZ5A and Pt30WZ15A, which provide conversions of approximately 80%-90% and a selectivity of 90%. These new findings enrich researcher knowledge of the effect of the binder on the catalyst shaping process and are useful in the production of industrial catalysts.
