HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD chara...HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.展开更多
Olefin alkylation of thiophenic sulfur process was carried out in model gasoline, using Hβ zeolites with different Si/Al2 ratios as catalysts. In particular, the influence of acid properties of Hβ zeolites on its ca...Olefin alkylation of thiophenic sulfur process was carried out in model gasoline, using Hβ zeolites with different Si/Al2 ratios as catalysts. In particular, the influence of acid properties of Hβ zeolites on its catalytic ability for the thiophene alkylation, xylene alkylation and hexene oligomerization was investigated. The results showed that the acidity of the Hβ zeolite was increased with the decrease of Si/Al2 ratio, but its catalytic ability was not always increased. In fact, it reached the maximal catalytic ability at Si/Al2 ratio of 66, and under the reaction conditions of 60 ℃, 1.5 MPa, WHSV 3.0 h^-1 and time on stream 2 h. At the ratio, the conversion of thiophene, xylene, and oligomerized hexene were 96.6%, 2.7% and 2.8%, respectively. An optimal Si/Al2 ratio exists for the catalytic performance of Hβ zeolite. By investigating the coke deposition of the used Hβ zeolite catalysts, it has been found that the optimal Si/Al2 ratio is attributed to the combined effect of the carbocation activation capability and the hydrogen transformation capability of the Hβ zeolite catalyst.展开更多
Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the...Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.展开更多
Shaped binderless ZSM-11 zeolite catalysts were synthesized via a dry-gel conversion technique from 70ZSM-11/30 SiO;mix extrudates. 1,6-hexanediamine combined with tetrabutylammonium bromide was proved to be the best ...Shaped binderless ZSM-11 zeolite catalysts were synthesized via a dry-gel conversion technique from 70ZSM-11/30 SiO;mix extrudates. 1,6-hexanediamine combined with tetrabutylammonium bromide was proved to be the best structure directing agent for the synthesis of the binderless ZSM-11 catalyst, without adding other alkaline materials. The 70HZSM-11/30 SiO;mix serials materials crystallized for different times were detected by X-ray diffraction（XRD）, nuclear magnetic resonance（NMR）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, scanning transmission electron microscopy–energy dispersive spectroscopy（STEM–EDS） techniques, and so on. In order to investigate the possible crystallization mechanism, the textural and structural properties of 70HZSM-11/30 SiO;mix serials samples were further characterized by N;adsorption–desorption. Acid properties were determined by temperature-programed desorption of NH;（NH;-TPD） and pyridine adsorption-infrared（Py-IR） measurements. In the alkylation of benzene with dimethyl ether, the serials catalysts exhibited different benzene conversions. 70HZSM-11/30 SiO;mix showed the lowest benzene conversion while sample 70HZSM-11/30 SiO;mix-6.5h synthesized only for 6.5h displayed a higher benzene conversion, even higher than the value over 70HZSM-11/30Al;O;mix. Extending the crystallization time, the obtained samples displayed the increased benzene conversion in general under the same reaction conditions. In the end, the relation of physicochemical properties with the reaction performance was investigated.展开更多
The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reac...The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reaction conditions the selectivity of alkenes to high-octane gasoline blending components was markedly enhanced and the formation of propane and butanes was greatly suppressed with the addition of DME.It was also found that the distribution of C5+ components was changed a lot with DME addition into the LPG feed.The formation of branched hydrocarbons (mainly C6 C8 i-paraffin) and multi-methyl substituted aromatics,which are high octane number gasoline blending components,was promoted significantly,while the content of n-paraffins and olefins in C5+ components was decreased obviously,indicating that in addition to the oligomerization,cracking,hydrogen-transfer and dehydrogenation-cyclization of alkenes,the methylation of the formed aromatics and olefins intermediates also plays an important role in determining the product distribution due to the high reactivity of surface methoxy groups formed by DME.And this process,in combination with the syngas-to-methanol/DME technology,provides an alternative way to the production of high-octane gasoline from coal,natural gas or renewable raw materials.展开更多
The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out ov...The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore（MRP） to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter（larger than 0.5 nm or with large side pockets/cups in the outside surface） and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%（>46.42% of the equilibrium conversion） under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al;ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity（isobutylene conversion） had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.展开更多
基金supported by K. C. Wong Education FoundationYouth Innovation Promotion Association of CAS (20120155)Dalian Eminent Young Scientist Program (2015R009)~~
基金the National Key Project for Basic Research of China(973 Project)(No.2005CB221403)the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant:DICP K2007D3)
文摘HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.
基金the National 973 Project of China(No.2005CB221403)the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant:DICP K2007D3)
文摘Olefin alkylation of thiophenic sulfur process was carried out in model gasoline, using Hβ zeolites with different Si/Al2 ratios as catalysts. In particular, the influence of acid properties of Hβ zeolites on its catalytic ability for the thiophene alkylation, xylene alkylation and hexene oligomerization was investigated. The results showed that the acidity of the Hβ zeolite was increased with the decrease of Si/Al2 ratio, but its catalytic ability was not always increased. In fact, it reached the maximal catalytic ability at Si/Al2 ratio of 66, and under the reaction conditions of 60 ℃, 1.5 MPa, WHSV 3.0 h^-1 and time on stream 2 h. At the ratio, the conversion of thiophene, xylene, and oligomerized hexene were 96.6%, 2.7% and 2.8%, respectively. An optimal Si/Al2 ratio exists for the catalytic performance of Hβ zeolite. By investigating the coke deposition of the used Hβ zeolite catalysts, it has been found that the optimal Si/Al2 ratio is attributed to the combined effect of the carbocation activation capability and the hydrogen transformation capability of the Hβ zeolite catalyst.
基金the National Natural Science Foundation of China(Grant No.20903088 and 21006104)
文摘Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.
基金supported by K.C.Wong Education FoundationDalian Eminent Young Scientist Program(2015R009)Natural Science Foundation of Heilongjiang Province(No.B2015006)
文摘Shaped binderless ZSM-11 zeolite catalysts were synthesized via a dry-gel conversion technique from 70ZSM-11/30 SiO;mix extrudates. 1,6-hexanediamine combined with tetrabutylammonium bromide was proved to be the best structure directing agent for the synthesis of the binderless ZSM-11 catalyst, without adding other alkaline materials. The 70HZSM-11/30 SiO;mix serials materials crystallized for different times were detected by X-ray diffraction（XRD）, nuclear magnetic resonance（NMR）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, scanning transmission electron microscopy–energy dispersive spectroscopy（STEM–EDS） techniques, and so on. In order to investigate the possible crystallization mechanism, the textural and structural properties of 70HZSM-11/30 SiO;mix serials samples were further characterized by N;adsorption–desorption. Acid properties were determined by temperature-programed desorption of NH;（NH;-TPD） and pyridine adsorption-infrared（Py-IR） measurements. In the alkylation of benzene with dimethyl ether, the serials catalysts exhibited different benzene conversions. 70HZSM-11/30 SiO;mix showed the lowest benzene conversion while sample 70HZSM-11/30 SiO;mix-6.5h synthesized only for 6.5h displayed a higher benzene conversion, even higher than the value over 70HZSM-11/30Al;O;mix. Extending the crystallization time, the obtained samples displayed the increased benzene conversion in general under the same reaction conditions. In the end, the relation of physicochemical properties with the reaction performance was investigated.
基金supported by the "Action Plan of CAS to Support China’s New and Strategic Industries with Science and Technology(2012-2014)"the "Knowledge Innovation Program of the Chinese Academy of Sciences(S201041)""Youth Innovation Promotion Association CAS(2012-2015)"
文摘The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reaction conditions the selectivity of alkenes to high-octane gasoline blending components was markedly enhanced and the formation of propane and butanes was greatly suppressed with the addition of DME.It was also found that the distribution of C5+ components was changed a lot with DME addition into the LPG feed.The formation of branched hydrocarbons (mainly C6 C8 i-paraffin) and multi-methyl substituted aromatics,which are high octane number gasoline blending components,was promoted significantly,while the content of n-paraffins and olefins in C5+ components was decreased obviously,indicating that in addition to the oligomerization,cracking,hydrogen-transfer and dehydrogenation-cyclization of alkenes,the methylation of the formed aromatics and olefins intermediates also plays an important role in determining the product distribution due to the high reactivity of surface methoxy groups formed by DME.And this process,in combination with the syngas-to-methanol/DME technology,provides an alternative way to the production of high-octane gasoline from coal,natural gas or renewable raw materials.
基金the financial support of K.C.Wong Education FoundationDalian Eminent Young Scientist Program(2015R009)
文摘The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore（MRP） to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter（larger than 0.5 nm or with large side pockets/cups in the outside surface） and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%（>46.42% of the equilibrium conversion） under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al;ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity（isobutylene conversion） had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.
