A novel process was proposed for the activation pretreatment of limonitic laterite ores by Na2CO3 roasting. Dechromization and dealumination kinetics of the laterite ores and the effect of particle size, Na2CO3-ore ma...A novel process was proposed for the activation pretreatment of limonitic laterite ores by Na2CO3 roasting. Dechromization and dealumination kinetics of the laterite ores and the effect of particle size, Na2CO3-ore mass ratio, and roasting temperature on Cr and Al extraction were studied. Experimental results indicate that the extraction rates of Cr and Al are up to 99%and 82%, respectively, under the optimal particle size of 44–74μm, Na2CO3-to-ore mass ratio of 0.6：1, and temperature of 1000 ℃. Dechromization within the range of 600–800 oC is controlled by the diffusion through the product layer with an apparent activation energy of 3.9 kJ/mol, and that it is controlled by the chemical reaction at the surface within the range of 900–1100 ℃ with an apparent activation energy of 54.3 kJ/mol. Besides, the Avrami diffusion controlled model with on apparent activation energy of 16.4 kJ/mol is most applicable for dealumination. Furthermore, 96.8%Ni and 95.6%Co could be extracted from the alkali-roasting residues in the subsequent pressure acid leaching process.展开更多
Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic a...Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.展开更多
We studied the factors affecting the framework aluminium distribution in the ZSM-5 structure by hydrothermal treatment under different conditions. (27)AlMASNMR, XPS and chemical analysis revealed that with steaming at...We studied the factors affecting the framework aluminium distribution in the ZSM-5 structure by hydrothermal treatment under different conditions. (27)AlMASNMR, XPS and chemical analysis revealed that with steaming at lower water vapor pressure, the framework aluminium located at the external surface is less stable. Steaming at higher water vapor pressure is beneficial in removing the framework Al in HZSM-5, and especially helpful in removing that located at the internal surface of HZSM-5. By changing steaming conditions, one may control the framework aluminium distribution in the HZSM-5 structure.展开更多
To get a better understanding of structural deactivation of ZSM-5/MOR during the catalytic cracking of n-heptane in the steam atmosphere, a comprehensive mechanism of hydrothermal dealumination was proposed through in...To get a better understanding of structural deactivation of ZSM-5/MOR during the catalytic cracking of n-heptane in the steam atmosphere, a comprehensive mechanism of hydrothermal dealumination was proposed through in-situ diffuse reflectance Fourier transform infrared spectroscopy(DRIFTS) in this work. The mechanism can be divided into two steps: firstly, the hydrolysis of four Al\\O bonds, and secondly, the self-healing of Si\\OH bonds accompanied with partial condensation of the extra-framework Al species. Accordingly, the kinetics of dealumination process has also been fully discussed. In the IR spectra, the range of 3450–3850 cm^(-1) could be deconvolved to distinguish the hydroxyl groups on the different position and calculate the consumption of each hydroxyl group during the reaction. Based on results from the in-situ DRIFTS, the kinetics of dealumination was hence developed and also in well agreement with the kinetics of deactivation of ZSM/MOR catalysts during the reaction in the presence of little coke deposits.展开更多
Dealuminated Y zeolite with high crystallinity is obtained from NaY zeolite by treatment with oxalic acid in a buffering system.The effect of dealumination conditions on the degree of dealumination and the crystallini...Dealuminated Y zeolite with high crystallinity is obtained from NaY zeolite by treatment with oxalic acid in a buffering system.The effect of dealumination conditions on the degree of dealumination and the crystallinity of the reformed zeolite is discussed.A mechanism for the reaction is proposed.展开更多
A series of different H-mordenites from acid leaching and steam calcination have beenmeasured with ^(29)Si NMR. Through analysis of these solid-state ^(29)Si NMR spectra, theresults related to dealumination process of...A series of different H-mordenites from acid leaching and steam calcination have beenmeasured with ^(29)Si NMR. Through analysis of these solid-state ^(29)Si NMR spectra, theresults related to dealumination process of mordenite are obtained. It is shown that mor-denite is combined by four kinds of non-equivalent Si (or Al) via oxygen bridges. The deal-umination order is T(1), T(2), T(4) and T(3). The dealuminated amount in the non-equivalentsites during different dealumination processes has also been discussed in detail.展开更多
In this study,we investigated Mo-impregnated H-MCM-22 catalysts(denoted Mo/M)for methanedehydroaromatization(MDA)to produce aromatics such as benzene and toluene(BT).We attemptedto improve the performance of the MDA c...In this study,we investigated Mo-impregnated H-MCM-22 catalysts(denoted Mo/M)for methanedehydroaromatization(MDA)to produce aromatics such as benzene and toluene(BT).We attemptedto improve the performance of the MDA catalysts by reducing the amount of Brönsted acidsites(BAS)of the H-MCM-22 supports via hydrothermal dealumination.Among the prepared catalysts,an optimal hydrothermal treatment(HT)of H-MCM-22 supports at 400℃,followed by Moimpregnation(denoted Mo/M_400),resulted in a reduced and optimal amount of BAS,along with acomparable Mo distribution to Mo/M.Further,Mo/M_400 enhanced BT formation rates(maximumBT formation rate of 5.23 vs.4.73 mmolBT·g^(−1)·h^(−1) for Mo/M);it appears that dealumination-inducedreduction in the quantity of BAS altered their spatial interaction with active Mo species,promotingBT and naphthalene formation.Interestingly,the lifetime of intermediate C_(2)(ethane and ethylene)formation was also improved for Mo/M_400.Rigorous coke analyses revealed that the decreasedcoke content in the aromatic-selective 10-membered-ring(10-MR)pores,as well as the ability ofthe 12-MR pores to accommodate coke deposits over a longer reaction time,improved the stabilityof Mo/M_400.Nonetheless,for all catalysts,the deactivations of BAS,and subsequently,the activeMo sites were mainly ascribed to coke deposition.The overall enhancement in MDA performance byMo/M_400 was attributed to the advantages of the optimally reduced BAS,allowing such performanceto surpass those of previously reported Mo-based catalysts.展开更多
Partially removing the framework Al atoms from low-silica aluminosilicates is an old but still challenging problem,because a high framework Al content generally induces lower acid strength and fast deactivation.An ina...Partially removing the framework Al atoms from low-silica aluminosilicates is an old but still challenging problem,because a high framework Al content generally induces lower acid strength and fast deactivation.An inappropriate dealumination method may cause structural collapse.The organic structuredirecting agent(OSDA)-free Beta zeolite is expected to serve as a green solid acid catalyst,but decreasing the Al content before being used as a catalyst is needed to enhance the stability and acid strength.Al2(SO4)3 was used to extract effectively the framework Al species from Al-rich OSDA-free Beta(Si/Al=4.3)under mild conditions,forming a natroalunite phase.The natroalunite phase was then selectively washed away with diluted NaOH solution,resulting in dealuminated zeolite(DeAl Beta)with a pure^(*)BEA phase and higher Si/Al ratios of 7.6-12.The dealuminated Beta zeolites were revealed to possess abundant mesopores while maintaining high crystallinity.The decrease of the total acid amount in DeAl Beta zeolites was accompanied by the enhancement of acid strength,resulting in higher selectivity of deeper cracking products and lower deactivation rate in the 1,3,5-triisopropylbenzene cracking reaction.The DeAl Beta also showed a high catalytic activity comparable to commercial nanosized Beta in the liquidphase Friedel-Crafts acylation,which was much higher than the parent Al-rich Beta.This study would provide a promising method for developing useful solid acid catalysts by the combination of OSDA-free synthesis and the eco-efficient dealumination process.展开更多
The hydrothermal stability of zeolites is an important factor being considered as it could restrict their scope of industrial application. Understanding the water-induced dealumination mechanism is crucial for improvi...The hydrothermal stability of zeolites is an important factor being considered as it could restrict their scope of industrial application. Understanding the water-induced dealumination mechanism is crucial for improving the hydrothermal stability of zeolites. Here a series of water-treated H-SSZ-13 samples under hydrothermal conditions was investigated by solid-state NMR methods and we found that dealumination was caused by the hydrolysis of the Al–O bond by water molecules under high temperature and pressure. The hydrolysis of the first Al–O bond could generate framework-associated Al species with a single framework aluminum hydroxyl. The sequential hydrolysis of four Al–O bonds could form the extra-framework aluminum (EFAL) species,which was prone to adsorbing near the Brønsted acid sites (BASs) by electrostatic interaction contributing to stabilizing the molecular sieve framework. Some of the BASs were perturbed by the framework or extra-framework aluminum hydroxyls which was represented by different signals in ^(1)H MAS NMR due to hydrogen-bonded interactions. The signals between 5 and 8 ppm in ^(1)H MAS NMR were attributed to the BASs perturbed by framework Al–OH (2.8 ppm),and correspondingly,BASs disturbed by extra-framework Al–OH (2.4 ppm) resulted in the signals appearing between 12 and 15 ppm. These clear attributions were facilitated by ^(1)H–^(1)H DQ-SQ and ^(1)H–^(27)Al S-RESPDOR MAS NMR. More than that,the partial or complete hydrolysis of the framework Al atoms was achieved uniformly by the water-treatment process under conditions of high temperature and pressure.展开更多
A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite ...A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved展开更多
In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeoli...In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeolites with acid treatment.Hydrocracking catalysts were prepared by loading WO_(3)onto these dealuminated Beta zeolites.It was shown that the surface SiO_(2)/Al_(2)O_(3)of selectively dealuminated Beta zeolites was higher than that of conventionally dealuminated samples for the same bulk SiO_(2)/Al_(2)O_(3),and the hydrogenation activity of the catalyst of the selectively dealuminated Beta zeolites was lower than that of conventionally dealuminated Beta zeolites.The experimental results for tetralin hydrocracking to BTX showed that the catalysts based on the selectively dealuminated Beta zeolites had higher BTX selectivity and lower coke formation rate than that the catalysts based on the conventionally dealuminated Beta zeolites.展开更多
The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benig...The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benign way.The catalysts commonly used for MTO process faces several challenges such as poor selectivity control,low hydrothermal stability and short lifetime.In the present study,we prepared a series of mordenite zeolites with variable Al contents(Si/Al molar ratios of 51−436)by a sequential dealumination treatment of air‐calcination and acid leaching.The textural properties,acidity and Al location before and after the dealumination treatment have been systematically studied and their effect on MTO especially the methanol to propylene(MTP)performance was thoroughly investigated.The mordenite zeolites with the Si/Al ratios over 150 selectively catalyzed methanol conversion in the MTP pathway,providing a high propylene selectivity of 63%and propylene/ethylene ratio of>10.Compared to the low‐silica MOR catalysts,highly dealuminated MOR showed much higher stability and longer lifetime,which can be further enhanced via harsh hydrothermal pretreatment.Furthermore,the lifetime was highly related to the crystal size along c‐axis.The excellent performance of highly dealuminated MOR is likely ascribed to the mesopores formed upon dealumination and the scarce Al sites located in the T sites shared by the 8‐member ring(MR)side pockets and 12‐MR pore channels.展开更多
Ce/BEA has the potential to be applied as a novel passive NO_(x)absorber(PNA)in the after-treatment of vehicles due to its considerable NO_(x)storage capacity.However,as a vehicle exhaust after-treatment material,it m...Ce/BEA has the potential to be applied as a novel passive NO_(x)absorber(PNA)in the after-treatment of vehicles due to its considerable NO_(x)storage capacity.However,as a vehicle exhaust after-treatment material,it must withstand the test of long-term hydrothermal aging.This work examined the deactivation mechanism of Ce/BEA during hydrothermal aging.3.0 wt%Ce/BEA was prepared using the ionexchange method,and then subjected to hydrothermal treatment at 650℃with 10%H_(2)O for 1-12 h to obtain samples with different aging extent.For comparison,the H-BEA support was aged under the same conditions.Brunauer-Emmett-Teller(BET)method,X-ray diffraction(XRD),NH_(3)temperature programmed reduction(NH_(3)-TPD),^(27)Al MAS nuclear magnetic resonance(^(27)Al MAS NMR),H_(2)temperature programmed reduction(H_(2)-TPR),and high resolution-transmission electron microscopy(HR-TEM)were performed to characterize the changes in PNA performance,structure,Ce species,and acidity.The HR-TEM and H_(2)-TPR results show that CeO_(x)particles appear after hydrothermal aging,which results from the detachment and aggregation of active Ce species.Based on the^(27)Al MAS NMR results,we conclude that BEA zeolite dealumination leads to the loss of acidic sites and the transformation of active Ce species on the acidic sites into the less active CeO_(x).This is the primary reason for the hydrothermal aging deactivation of Ce/BEA.展开更多
Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite...Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite. The characterization results revealed the amount of aluminum in the zeolitic framework, the crystallinity of the ZSM-5 zeolite, and the Si/Al ratio affected the formation of Bronsted acid sites. The number of the Bronsted acid sites on the catalyst active sites is important in the olefin conversion to liquid hydrocarbons.展开更多
This article mainly worked on methods to reduce side reactions of the de-ethylating type catalyst for xylene isomerization. In laboratory the de-ethylating type catalyst for xylene isomerization was subjected to steam...This article mainly worked on methods to reduce side reactions of the de-ethylating type catalyst for xylene isomerization. In laboratory the de-ethylating type catalyst for xylene isomerization was subjected to steam treatment at different temperatures and durations to achieve dealumination of the ZSM-5 zeolite to some extent, which could affect the change in BrФnsted acid content to decrease xylene loss along with reduction of side reactions. Test results showed that the degree for reducing side reactions by steam treatment depended upon two important parameters-treating temperature and duration. The optimal condition required treating the catalyst at 500℃ for 8 hours.展开更多
A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FC...A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FCC catalysts to produce high-octane gasoline and light olefins, was developed. With the DOCR and DOCP catalysts containing the ZRP zeolite modified by phosphorus-incorporation as the octaneenhancing catalysts, the commercial trial was carried out in a 0.8Mt/a RFCC unit with a feedstock composed of Daqing atmospheric residue. As compared to the base catalyst, the LPG+gasoline+LCO product yield obtained from this catalyst was increased by 0.53m%. Meanwhile, the RON and MON of gasoline was increased by 1.4 and 2.4 units, respectively. The higher increment of MON is attributable to the higher isoparaffines content in gasoline. This result indicates that the ZRP zeolite possesses higher isomerization selectivity.展开更多
NaY zeolite was modified through dealumination with oxalic acid,and the HY zeolite was obtained by calcination of the modified NaY zeolite.The zeolite molding process was carried out at ambient temperature(25℃),and t...NaY zeolite was modified through dealumination with oxalic acid,and the HY zeolite was obtained by calcination of the modified NaY zeolite.The zeolite molding process was carried out at ambient temperature(25℃),and the influence of solid/fuel mass ratio and adsorptive desulfurization time on the HY zeolite were investigated through tests on static selective adsorptive desulfurization of FCC gasoline containing organic sulfur compounds(with a S content=135 ppm).The sulfur content and sulphide types in the FCC gasoline were analyzed by a GC 2010 sulfur analyzer and a GC-SCD chromatograph.The test results showed that the molded HY zeolite was better than the unmolded HY zeolite.At a static adsorptive desulfurization time on the molded HY zeolite equating to 6 hours,a solid/fuel mass ratio of 1:3,the sulfur content of FCC gasoline was decreased to 30 ppm,and the desulfurization rate was equal to 78%.When the breakthrough point of the molded HY was equal to 50 ppm,the molded HY zeolite was capable of adsorbing 4.86 mg of sulfur per gram of adsorbent.And the regeneration rate of molded HY zeolite was equal to 98%.展开更多
Effects of hydrochloride acid dealumination of mordenite(MOR) catalysts for the synthesis of 1-phenyl-1-xylyl ethane(PXE) were investigated. The structure and acidity of catalysts were characterized by XRD, BET, XRF, ...Effects of hydrochloride acid dealumination of mordenite(MOR) catalysts for the synthesis of 1-phenyl-1-xylyl ethane(PXE) were investigated. The structure and acidity of catalysts were characterized by XRD, BET, XRF, FT-IR, 27Al NMR and NH3-TPD techniques. The catalytic performance of the acid-treated MOR zeolites was studied through using the alkylation of o-xylene with styrene. The test results showed that the strength of remaining Br?nsted acid sites increased despite the reduction of total number of acid sites after dealumination, and the micropores of HMOR were slightly enlarged coupled with the formation of secondary mesopores. Additionally, the modified HMOR zeolites showed longer catalyst life with the styrene conversion rate retained. Among the catalysts employed in this study, the modified mordenite that was dealuminated by HCl(2 mol/L) could be used repeatedly without significant loss of activity and selectivity during six catalytic runs, which have been ascribed to its specific acidity and structural properties.展开更多
This work describes the development of a process to produce zeolite X from mined kaolin clay from Kono-Boue and Chokocho, Rivers State, Nigeria. The procedures involved the beneficiation of the raw kaolin and calcinat...This work describes the development of a process to produce zeolite X from mined kaolin clay from Kono-Boue and Chokocho, Rivers State, Nigeria. The procedures involved the beneficiation of the raw kaolin and calcinations at 850<span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span>C, to transform the kaolin to a more reactive metakaolin. Afterwards, the extremely reactive metakaolin was purge with sulphuric acid to obtain the much needed silica-alumina ratio for zeolite X synthesis. An alkaline fusion stage was then carried out to transform the metakaolin into zeolite by mixing with aqueous NaOH to form gel then allowed to stay for a duration of seven days at room temperature. The samples were then charged into a propylene container and placed in an oven at a temperature of 100<span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span>C for the reaction to take place for 6 h. Identification of the crystalline phases by X-ray Diffraction (XRD), chemical/elemental compositions by X-ray Fluorescence (XRF)/Energy Dispersive Spectroscopic analyses (EDS), surface morphology by Scanning Electron Microscopy (SEM) and molecular vibration of units by Fourier Transform Infrared Spectrophotometry (FT-IR) were done. The results showed that the zeolite synthesized from Chokocho kaolin (CK) was more crystalline/larger with sharper peaks on both XRD and FTIR than that from Kono-Boue. This was also supported by slightly rougher surface morphology of CK over KK on SEM. XRF Si:Al ratios of 10.73 and 14.36 were obtained for KK and CK respectively. EDS results supported the XRF ratios. Sharper zeolitic characteristic O-H stretching bands at 3488 and 3755 cm<sup>-1</sup> were recorded for CK than KK. However, both results showed that zeolite X have been produced from both Kono-Boue and Chokocho kaolin clays respectively.展开更多
基金Project(51125018)supported by the National Natural Science Foundation for Distinguished Young Scholars of ChinaProject(51204153)supported by the National Natural Science Foundation of ChinaProject(2011BAC06B07)supported by the National High Technology Research and Development Program,China
文摘A novel process was proposed for the activation pretreatment of limonitic laterite ores by Na2CO3 roasting. Dechromization and dealumination kinetics of the laterite ores and the effect of particle size, Na2CO3-ore mass ratio, and roasting temperature on Cr and Al extraction were studied. Experimental results indicate that the extraction rates of Cr and Al are up to 99%and 82%, respectively, under the optimal particle size of 44–74μm, Na2CO3-to-ore mass ratio of 0.6：1, and temperature of 1000 ℃. Dechromization within the range of 600–800 oC is controlled by the diffusion through the product layer with an apparent activation energy of 3.9 kJ/mol, and that it is controlled by the chemical reaction at the surface within the range of 900–1100 ℃ with an apparent activation energy of 54.3 kJ/mol. Besides, the Avrami diffusion controlled model with on apparent activation energy of 16.4 kJ/mol is most applicable for dealumination. Furthermore, 96.8%Ni and 95.6%Co could be extracted from the alkali-roasting residues in the subsequent pressure acid leaching process.
基金partly supported by the International Science Foundation~~
文摘Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.
文摘We studied the factors affecting the framework aluminium distribution in the ZSM-5 structure by hydrothermal treatment under different conditions. (27)AlMASNMR, XPS and chemical analysis revealed that with steaming at lower water vapor pressure, the framework aluminium located at the external surface is less stable. Steaming at higher water vapor pressure is beneficial in removing the framework Al in HZSM-5, and especially helpful in removing that located at the internal surface of HZSM-5. By changing steaming conditions, one may control the framework aluminium distribution in the HZSM-5 structure.
基金Supported by the National Key Research and Development Program of China(2016YFA0202900)the National Natural Science Foundation of China(91434123,21622606)+1 种基金Zhejiang Provincial Natural Science Foundation of China(LR18B060001)the Fundamental Research Funds for the Central Universities
文摘To get a better understanding of structural deactivation of ZSM-5/MOR during the catalytic cracking of n-heptane in the steam atmosphere, a comprehensive mechanism of hydrothermal dealumination was proposed through in-situ diffuse reflectance Fourier transform infrared spectroscopy(DRIFTS) in this work. The mechanism can be divided into two steps: firstly, the hydrolysis of four Al\\O bonds, and secondly, the self-healing of Si\\OH bonds accompanied with partial condensation of the extra-framework Al species. Accordingly, the kinetics of dealumination process has also been fully discussed. In the IR spectra, the range of 3450–3850 cm^(-1) could be deconvolved to distinguish the hydroxyl groups on the different position and calculate the consumption of each hydroxyl group during the reaction. Based on results from the in-situ DRIFTS, the kinetics of dealumination was hence developed and also in well agreement with the kinetics of deactivation of ZSM/MOR catalysts during the reaction in the presence of little coke deposits.
基金supported by The National Natural Science Foundation(No.29473088)
文摘Dealuminated Y zeolite with high crystallinity is obtained from NaY zeolite by treatment with oxalic acid in a buffering system.The effect of dealumination conditions on the degree of dealumination and the crystallinity of the reformed zeolite is discussed.A mechanism for the reaction is proposed.
文摘A series of different H-mordenites from acid leaching and steam calcination have beenmeasured with ^(29)Si NMR. Through analysis of these solid-state ^(29)Si NMR spectra, theresults related to dealumination process of mordenite are obtained. It is shown that mor-denite is combined by four kinds of non-equivalent Si (or Al) via oxygen bridges. The deal-umination order is T(1), T(2), T(4) and T(3). The dealuminated amount in the non-equivalentsites during different dealumination processes has also been discussed in detail.
文摘In this study,we investigated Mo-impregnated H-MCM-22 catalysts(denoted Mo/M)for methanedehydroaromatization(MDA)to produce aromatics such as benzene and toluene(BT).We attemptedto improve the performance of the MDA catalysts by reducing the amount of Brönsted acidsites(BAS)of the H-MCM-22 supports via hydrothermal dealumination.Among the prepared catalysts,an optimal hydrothermal treatment(HT)of H-MCM-22 supports at 400℃,followed by Moimpregnation(denoted Mo/M_400),resulted in a reduced and optimal amount of BAS,along with acomparable Mo distribution to Mo/M.Further,Mo/M_400 enhanced BT formation rates(maximumBT formation rate of 5.23 vs.4.73 mmolBT·g^(−1)·h^(−1) for Mo/M);it appears that dealumination-inducedreduction in the quantity of BAS altered their spatial interaction with active Mo species,promotingBT and naphthalene formation.Interestingly,the lifetime of intermediate C_(2)(ethane and ethylene)formation was also improved for Mo/M_400.Rigorous coke analyses revealed that the decreasedcoke content in the aromatic-selective 10-membered-ring(10-MR)pores,as well as the ability ofthe 12-MR pores to accommodate coke deposits over a longer reaction time,improved the stabilityof Mo/M_400.Nonetheless,for all catalysts,the deactivations of BAS,and subsequently,the activeMo sites were mainly ascribed to coke deposition.The overall enhancement in MDA performance byMo/M_400 was attributed to the advantages of the optimally reduced BAS,allowing such performanceto surpass those of previously reported Mo-based catalysts.
基金supported by the National Natural Science Foundation of China(Grant No.21872052,21533002,and 21972044)the Ministry of Science and Technology of the People’s Republic of China(2016YFA0202804)the Fundamental Research Funds for the Central Universities.
文摘Partially removing the framework Al atoms from low-silica aluminosilicates is an old but still challenging problem,because a high framework Al content generally induces lower acid strength and fast deactivation.An inappropriate dealumination method may cause structural collapse.The organic structuredirecting agent(OSDA)-free Beta zeolite is expected to serve as a green solid acid catalyst,but decreasing the Al content before being used as a catalyst is needed to enhance the stability and acid strength.Al2(SO4)3 was used to extract effectively the framework Al species from Al-rich OSDA-free Beta(Si/Al=4.3)under mild conditions,forming a natroalunite phase.The natroalunite phase was then selectively washed away with diluted NaOH solution,resulting in dealuminated zeolite(DeAl Beta)with a pure^(*)BEA phase and higher Si/Al ratios of 7.6-12.The dealuminated Beta zeolites were revealed to possess abundant mesopores while maintaining high crystallinity.The decrease of the total acid amount in DeAl Beta zeolites was accompanied by the enhancement of acid strength,resulting in higher selectivity of deeper cracking products and lower deactivation rate in the 1,3,5-triisopropylbenzene cracking reaction.The DeAl Beta also showed a high catalytic activity comparable to commercial nanosized Beta in the liquidphase Friedel-Crafts acylation,which was much higher than the parent Al-rich Beta.This study would provide a promising method for developing useful solid acid catalysts by the combination of OSDA-free synthesis and the eco-efficient dealumination process.
基金supported by the National Natural Science Foundation of China(22022202,21972142,21991092,21991090)Dalian Outstanding Young Scientist Foundation(2021RJ01).
文摘The hydrothermal stability of zeolites is an important factor being considered as it could restrict their scope of industrial application. Understanding the water-induced dealumination mechanism is crucial for improving the hydrothermal stability of zeolites. Here a series of water-treated H-SSZ-13 samples under hydrothermal conditions was investigated by solid-state NMR methods and we found that dealumination was caused by the hydrolysis of the Al–O bond by water molecules under high temperature and pressure. The hydrolysis of the first Al–O bond could generate framework-associated Al species with a single framework aluminum hydroxyl. The sequential hydrolysis of four Al–O bonds could form the extra-framework aluminum (EFAL) species,which was prone to adsorbing near the Brønsted acid sites (BASs) by electrostatic interaction contributing to stabilizing the molecular sieve framework. Some of the BASs were perturbed by the framework or extra-framework aluminum hydroxyls which was represented by different signals in ^(1)H MAS NMR due to hydrogen-bonded interactions. The signals between 5 and 8 ppm in ^(1)H MAS NMR were attributed to the BASs perturbed by framework Al–OH (2.8 ppm),and correspondingly,BASs disturbed by extra-framework Al–OH (2.4 ppm) resulted in the signals appearing between 12 and 15 ppm. These clear attributions were facilitated by ^(1)H–^(1)H DQ-SQ and ^(1)H–^(27)Al S-RESPDOR MAS NMR. More than that,the partial or complete hydrolysis of the framework Al atoms was achieved uniformly by the water-treatment process under conditions of high temperature and pressure.
基金supported by the National Natural Science Foundation of China(21276041,U1610104)the Chinese Ministry of Education via the Program for New Century Excellent Talents in University(NCET-12-0079)~~
文摘A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved
文摘In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeolites with acid treatment.Hydrocracking catalysts were prepared by loading WO_(3)onto these dealuminated Beta zeolites.It was shown that the surface SiO_(2)/Al_(2)O_(3)of selectively dealuminated Beta zeolites was higher than that of conventionally dealuminated samples for the same bulk SiO_(2)/Al_(2)O_(3),and the hydrogenation activity of the catalyst of the selectively dealuminated Beta zeolites was lower than that of conventionally dealuminated Beta zeolites.The experimental results for tetralin hydrocracking to BTX showed that the catalysts based on the selectively dealuminated Beta zeolites had higher BTX selectivity and lower coke formation rate than that the catalysts based on the conventionally dealuminated Beta zeolites.
文摘The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benign way.The catalysts commonly used for MTO process faces several challenges such as poor selectivity control,low hydrothermal stability and short lifetime.In the present study,we prepared a series of mordenite zeolites with variable Al contents(Si/Al molar ratios of 51−436)by a sequential dealumination treatment of air‐calcination and acid leaching.The textural properties,acidity and Al location before and after the dealumination treatment have been systematically studied and their effect on MTO especially the methanol to propylene(MTP)performance was thoroughly investigated.The mordenite zeolites with the Si/Al ratios over 150 selectively catalyzed methanol conversion in the MTP pathway,providing a high propylene selectivity of 63%and propylene/ethylene ratio of>10.Compared to the low‐silica MOR catalysts,highly dealuminated MOR showed much higher stability and longer lifetime,which can be further enhanced via harsh hydrothermal pretreatment.Furthermore,the lifetime was highly related to the crystal size along c‐axis.The excellent performance of highly dealuminated MOR is likely ascribed to the mesopores formed upon dealumination and the scarce Al sites located in the T sites shared by the 8‐member ring(MR)side pockets and 12‐MR pore channels.
基金supported the National Key R&D Program of China(2021YFB3503200)the Innovative Research Groups of the National Natural Science Foundation of China(51921004)+1 种基金Young Elite Scientists Sponsorship Program by CAST(2021QNRC001)the Key R&D Project of Shandong Province(2021CXGC010703,2022CXGC020311)。
文摘Ce/BEA has the potential to be applied as a novel passive NO_(x)absorber(PNA)in the after-treatment of vehicles due to its considerable NO_(x)storage capacity.However,as a vehicle exhaust after-treatment material,it must withstand the test of long-term hydrothermal aging.This work examined the deactivation mechanism of Ce/BEA during hydrothermal aging.3.0 wt%Ce/BEA was prepared using the ionexchange method,and then subjected to hydrothermal treatment at 650℃with 10%H_(2)O for 1-12 h to obtain samples with different aging extent.For comparison,the H-BEA support was aged under the same conditions.Brunauer-Emmett-Teller(BET)method,X-ray diffraction(XRD),NH_(3)temperature programmed reduction(NH_(3)-TPD),^(27)Al MAS nuclear magnetic resonance(^(27)Al MAS NMR),H_(2)temperature programmed reduction(H_(2)-TPR),and high resolution-transmission electron microscopy(HR-TEM)were performed to characterize the changes in PNA performance,structure,Ce species,and acidity.The HR-TEM and H_(2)-TPR results show that CeO_(x)particles appear after hydrothermal aging,which results from the detachment and aggregation of active Ce species.Based on the^(27)Al MAS NMR results,we conclude that BEA zeolite dealumination leads to the loss of acidic sites and the transformation of active Ce species on the acidic sites into the less active CeO_(x).This is the primary reason for the hydrothermal aging deactivation of Ce/BEA.
文摘Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite. The characterization results revealed the amount of aluminum in the zeolitic framework, the crystallinity of the ZSM-5 zeolite, and the Si/Al ratio affected the formation of Bronsted acid sites. The number of the Bronsted acid sites on the catalyst active sites is important in the olefin conversion to liquid hydrocarbons.
文摘This article mainly worked on methods to reduce side reactions of the de-ethylating type catalyst for xylene isomerization. In laboratory the de-ethylating type catalyst for xylene isomerization was subjected to steam treatment at different temperatures and durations to achieve dealumination of the ZSM-5 zeolite to some extent, which could affect the change in BrФnsted acid content to decrease xylene loss along with reduction of side reactions. Test results showed that the degree for reducing side reactions by steam treatment depended upon two important parameters-treating temperature and duration. The optimal condition required treating the catalyst at 500℃ for 8 hours.
文摘A hetero-crystalline seeding method to prepare a unique MFI type zeolite with mesopores of ca. 4 nm diameter designated as the ZRP zeolite, which possesses high stability and selectivity and is used as component of FCC catalysts to produce high-octane gasoline and light olefins, was developed. With the DOCR and DOCP catalysts containing the ZRP zeolite modified by phosphorus-incorporation as the octaneenhancing catalysts, the commercial trial was carried out in a 0.8Mt/a RFCC unit with a feedstock composed of Daqing atmospheric residue. As compared to the base catalyst, the LPG+gasoline+LCO product yield obtained from this catalyst was increased by 0.53m%. Meanwhile, the RON and MON of gasoline was increased by 1.4 and 2.4 units, respectively. The higher increment of MON is attributable to the higher isoparaffines content in gasoline. This result indicates that the ZRP zeolite possesses higher isomerization selectivity.
文摘NaY zeolite was modified through dealumination with oxalic acid,and the HY zeolite was obtained by calcination of the modified NaY zeolite.The zeolite molding process was carried out at ambient temperature(25℃),and the influence of solid/fuel mass ratio and adsorptive desulfurization time on the HY zeolite were investigated through tests on static selective adsorptive desulfurization of FCC gasoline containing organic sulfur compounds(with a S content=135 ppm).The sulfur content and sulphide types in the FCC gasoline were analyzed by a GC 2010 sulfur analyzer and a GC-SCD chromatograph.The test results showed that the molded HY zeolite was better than the unmolded HY zeolite.At a static adsorptive desulfurization time on the molded HY zeolite equating to 6 hours,a solid/fuel mass ratio of 1:3,the sulfur content of FCC gasoline was decreased to 30 ppm,and the desulfurization rate was equal to 78%.When the breakthrough point of the molded HY was equal to 50 ppm,the molded HY zeolite was capable of adsorbing 4.86 mg of sulfur per gram of adsorbent.And the regeneration rate of molded HY zeolite was equal to 98%.
基金the financial supports of the National Natural Science Foundation of China (Grant No. 21306023, 21376051, 21106017 and 51077013)the Fund Project for Transformation of Scientific and Technological Achievements of Jiangsu Province (Grant No. BA2011086)+2 种基金the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100092120047)the Key Program for the Scientific Research Guiding Fund of Basic Scientific Research Operation Expenditure of Southeast University (Grant No. 3207043101)the Instrumental Analysis Fund of Southeast University
文摘Effects of hydrochloride acid dealumination of mordenite(MOR) catalysts for the synthesis of 1-phenyl-1-xylyl ethane(PXE) were investigated. The structure and acidity of catalysts were characterized by XRD, BET, XRF, FT-IR, 27Al NMR and NH3-TPD techniques. The catalytic performance of the acid-treated MOR zeolites was studied through using the alkylation of o-xylene with styrene. The test results showed that the strength of remaining Br?nsted acid sites increased despite the reduction of total number of acid sites after dealumination, and the micropores of HMOR were slightly enlarged coupled with the formation of secondary mesopores. Additionally, the modified HMOR zeolites showed longer catalyst life with the styrene conversion rate retained. Among the catalysts employed in this study, the modified mordenite that was dealuminated by HCl(2 mol/L) could be used repeatedly without significant loss of activity and selectivity during six catalytic runs, which have been ascribed to its specific acidity and structural properties.
文摘This work describes the development of a process to produce zeolite X from mined kaolin clay from Kono-Boue and Chokocho, Rivers State, Nigeria. The procedures involved the beneficiation of the raw kaolin and calcinations at 850<span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span>C, to transform the kaolin to a more reactive metakaolin. Afterwards, the extremely reactive metakaolin was purge with sulphuric acid to obtain the much needed silica-alumina ratio for zeolite X synthesis. An alkaline fusion stage was then carried out to transform the metakaolin into zeolite by mixing with aqueous NaOH to form gel then allowed to stay for a duration of seven days at room temperature. The samples were then charged into a propylene container and placed in an oven at a temperature of 100<span style="font-family:Verdana, Helvetica, Arial;white-space:normal;background-color:#FFFFFF;">°</span>C for the reaction to take place for 6 h. Identification of the crystalline phases by X-ray Diffraction (XRD), chemical/elemental compositions by X-ray Fluorescence (XRF)/Energy Dispersive Spectroscopic analyses (EDS), surface morphology by Scanning Electron Microscopy (SEM) and molecular vibration of units by Fourier Transform Infrared Spectrophotometry (FT-IR) were done. The results showed that the zeolite synthesized from Chokocho kaolin (CK) was more crystalline/larger with sharper peaks on both XRD and FTIR than that from Kono-Boue. This was also supported by slightly rougher surface morphology of CK over KK on SEM. XRF Si:Al ratios of 10.73 and 14.36 were obtained for KK and CK respectively. EDS results supported the XRF ratios. Sharper zeolitic characteristic O-H stretching bands at 3488 and 3755 cm<sup>-1</sup> were recorded for CK than KK. However, both results showed that zeolite X have been produced from both Kono-Boue and Chokocho kaolin clays respectively.
