Direct conversion of methane to benzene or other valuable chemicals is a very promising process for the efficient application of natural gas. Compared with conversion processes that require oxidants, non-oxidative dir...Direct conversion of methane to benzene or other valuable chemicals is a very promising process for the efficient application of natural gas. Compared with conversion processes that require oxidants, non-oxidative direct conversion is more attractive due to high selectivity to the target product. In this paper, an alternative route for methane dehydrogenation and selective conversion to benzene and hydrogen without the participation of oxygen is discussed. A brief review of the catalysts used in methane dehydroaromatization （MDA） is first given, followed by our current understanding of the location and the active phase of Mo species, the reaction mechanism, the mechanism of carbonaceous deposit and the deactivation of Mo/zeolite catalysts are systematically discussed. Ways to improve the catalytic activity and stability are described in detail based on catalyst and reaction as well as reactor design. Future prospects for methane dehydroaromatization process are also presented.展开更多
Long-term stability test of Mo/HZSM-5-N catalysts（HZSM-5-N stands for nano-sized HZSM-5） in methane dehydroaromatization（MDA）reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 100...Long-term stability test of Mo/HZSM-5-N catalysts（HZSM-5-N stands for nano-sized HZSM-5） in methane dehydroaromatization（MDA）reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 1000 h.During this test,methane conversion ranges from 13% to 16%,and mean yield to aromatics（i.e.benzene and naphthalene） exceeds 10%.N2-physisorption,XRD,NMR and TPO measurements were performed for the used Mo/HZSM-5 catalysts and coke deposition,and the results revealed that the periodic hydrogenation can effectively suppress coke deposition by removing the inert aromatic-type coke,thus ensuring Mo/HZSM-5 partly maintained its activity even in the presence of large amount of coke deposition.The effect of zeolite particle size on the catalytic activity was also explored,and the results showed that the nano-sized zeolite with low diffusion resistance performed better.It is recognized that the size effect was enhanced by reaction time,and it became more remarkable in a long-term MDA reaction even at a low space velocity.展开更多
Three industry-supplied, well-shaped Mo/HZSM-5 catalysts, two binder-added and one binder-free, were tested for the first time in methane dehydroaromatization to benzene at 1073 K and 10000 mL/（g·h） in periodic...Three industry-supplied, well-shaped Mo/HZSM-5 catalysts, two binder-added and one binder-free, were tested for the first time in methane dehydroaromatization to benzene at 1073 K and 10000 mL/（g·h） in periodic CH4-H2 switch operation mode, and their catalytic performances were compared with those of three self-prepared, binder-free powder Mo/HZSM-5 catalysts. XRD, 27Al NMR, SEM, BET and NH3-TPD characterizations of all the catalysts show that the zeolites in the two binder-added catalysts are comparable to those in the three binder-free powder catalysts in crystallinity, crystal size, micropore volume and Br{／o}nsted acidity. The test results, on the other hand, show that the catalytic performances of the two binder-added catalysts are worse than those of the four binder-free catalysts on both catalyst mass and zeolite mass bases. Then, TPO and BET measurements of all spent samples were conducted to get a deep insight into the negative effects of binder addition, and the results suggest that the binder additives functioned mainly to enhance the polyaromatization of formed aromatics to coke on their external surfaces and consequently lower the catalysts＇ benzene formation activity and selectivity.展开更多
For direct gas to liquid（GTL）,a novel process producing energy sources for methane dehydroaromatization is needed.Supporting MoO3 on H-MFI zeolite shows the high catalytic capacity and a selective activity for dehyd...For direct gas to liquid（GTL）,a novel process producing energy sources for methane dehydroaromatization is needed.Supporting MoO3 on H-MFI zeolite shows the high catalytic capacity and a selective activity for dehydroaromatization of methane to benzene at 973 K in a fixed bed reactor.On the other hand,deactivation by coke on the active sites in all the catalysts is formed during the reaction.H2 co-feed suppressed the deactivation,which is probably due to the decrease in coking amount.Mo K-edge X-ray absorption fine structure（XAFS） results showed the formation of dispersed Mo2C species with low crystallinity after dehydroaromatization.Mo LIII-edge XANES（X-ray absorption near-edge structure） indicated the formation of active Mo species including Mo2C and Mo-oxycarbide（MoOxCy）,where the redox state should be independent in the absence/presence of H2.It is concluded that Mo-oxycarbide species act as highly active species,and their stability affected the durable activity in the presence of H2.展开更多
The promotion effect of CO in methane dehydroaromatization was investigated using ^13CO probe molecules. By alternative injection of ^13CO to the methane feed, the distribution of ^13CxC6-xH6（x= 0-3） products change...The promotion effect of CO in methane dehydroaromatization was investigated using ^13CO probe molecules. By alternative injection of ^13CO to the methane feed, the distribution of ^13CxC6-xH6（x= 0-3） products changed significantly, confirming the participation of ^13CO in the reaction network. The addition of ^13CO did not change the conversion of CH4 but improved slightly the durability of the methane dehydroaromatization （MDA） reaction, which might be caused by the interaction of the dissociated oxygen species and the deposited carbon species. The ratio of ^13CxC6-xH6 （x = 0-3） varied with the time on stream, which was determined by the competitive reactions of methane decomposition and ^13CO dissociation.展开更多
The effect of dimethyl ether (DME) co-feed on the catalytic performance of methane dehy-droaromatization (MDA) over 6Mo/HZSM-5 catalyst was investigated as a function of DME concentration under reaction conditions of ...The effect of dimethyl ether (DME) co-feed on the catalytic performance of methane dehy-droaromatization (MDA) over 6Mo/HZSM-5 catalyst was investigated as a function of DME concentration under reaction conditions of T=1023 K, p=101 kPa and SV=1500 ml/(g·h). A high benzene yield was obtained and the stability of the catalyst was improved by adding 1.5%DME to the CH4 feed. The C6H6 yield was as high as ca. 10% even after reaction for 6 h. The stability of the catalyst was further improved when DME concentration in the co-feed gas was increased to an appropriate value. TGA and TPO results of the used 6Mo/HZSM-5 catalyst showed that the amount of coke on the used catalyst was reduced and the chemical nature of the coke was changed. When 1.5%DME was added to the CH4 feed, the coke formed on the catalyst could be burned off more easily than that when only CH4 was used as reactant. It is supposed that the oxygen in DME may play a role in preventing the coke burnt off at lower temperature from transforming into the coke burnt off at higher temperature, which results in the improvement of the stability of the catalyst.展开更多
Methane dehydroaromatization was studied over Mo/SiO2 and Mo/HZSM-5 with different Mo loadings(2, 5, 10 wt%) at 973 K and 1023 K in a recirculating batch reactor. H2 pretreatment at 1023 K prior to methane activation ...Methane dehydroaromatization was studied over Mo/SiO2 and Mo/HZSM-5 with different Mo loadings(2, 5, 10 wt%) at 973 K and 1023 K in a recirculating batch reactor. H2 pretreatment at 1023 K prior to methane activation has significantly improved the catalyst activity with increase in Mo loading and reduced the induction time on benzene formation in both Mo/SiO2 and Mo/HZSM-5. 10 wt% Mo/HZSM-5 gave a maximum methane conversion of 19% and ~67% benzene selectivity at 1023 K. The XRD analysis of used catalysts revealed that the Mo O3 species were converted to β-Mo2C phase. Studies on Mo/SiO2 catalysts showed that benzene was formed even in the absence of acidic zeolite sites. Reactions of ethylene in the presence of pure silica, HZSM-5 and in a blank reactor revealed that conversion of ethylene to aromatics was similar in case of the blank reactor and silica. Thus, it is believed that molybdenum carbide sites act as active sites only for C–H bond activation of methane and ethylene formation. Even though, ethylene can undergo subsequent oligomerization without any catalytic aid to form benzene at973 K and above addition of acidic zeolites improved the selectivity of benzene.展开更多
The dehydroaramatization of methane over W-supported ZSM-5 with varying degrees of Li+ ion-exchanged catalysts was studied with and without oxygen at 1073 K and atmospheric pressure. Catalyst activity and stability we...The dehydroaramatization of methane over W-supported ZSM-5 with varying degrees of Li+ ion-exchanged catalysts was studied with and without oxygen at 1073 K and atmospheric pressure. Catalyst activity and stability were found to be influenced by the catalyst acidity related to Bronsted acid sites and by the presence of oxygen in the feed. The NH3-TPD and FTIR-pyridine results demonstrated that partially exchanged of H+ ions by Li+ into the W/HZSM-5 catalysts could be used to control the amount of strong acid sites on the catalyst surface. Without oxygen, the 3WHLi-Z (5:1) catalyst that has strong acid sites equal to nearly 74% of the original strong acid sites in the parent HZSM-5 exhibited the highest methane conversion and selectivity towards aromatics. However, the catalyst deactivated in a five hour period. In the presence of oxygen, the catalyst activity and stability could be improved further. The results of this study revealed that a suitable amount of strong Bronsted acid sites as well as oxygen addition in the feed increased the catalyst activity and stability. The 3WHLi-Z(5:1) catalyst exhibited improved performance in the dehydroaromatization of methane.展开更多
The effect of addition of Ru and Pd to Mo/HZSM-5 catalysts used in the dehydroaromatization of methane was investigated. Catalytic tests and temperature-programmed oxidation results showed that Pd-based catalysts were...The effect of addition of Ru and Pd to Mo/HZSM-5 catalysts used in the dehydroaromatization of methane was investigated. Catalytic tests and temperature-programmed oxidation results showed that Pd-based catalysts were more selective to naphthalene and suffered strong deactivation. The presence of Ru improved the activity and stability, with a decrease in the carbonaceous deposit probably because of a mechanism of protection of the Mo2C surface.展开更多
A pilot-scale methane dehydroaromatization–H_2regeneration fluidized bed system(MDARS)was developed.In the MDARS,the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help ...A pilot-scale methane dehydroaromatization–H_2regeneration fluidized bed system(MDARS)was developed.In the MDARS,the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help of a catalyst feeder allowed methane dehydroaromatization(MDA)and H_2regeneration to be carried out simultaneously,which is good for maintaining a stable MDA catalytic activity.A fixed bed reactor(FB)and a single fluidized bed reactor(SFB)were also used for a comparative study.The experimental results showed that the catalytic activity in the MDARS was more stable than that in the FB and SFB reactors.The effects of some parameters of MDARS on the CH_4conversion and product selectivity were investigated.To verify the feasibility and reliability of the MDARS,an eight-hour long-term test was carried out,which demonstrated that the operation of the MDARS was stable and that the catalytic activity remained stable throughout the entire experimental period.展开更多
基金the National Natural Science Foundation of China(No.21103181)
文摘Direct conversion of methane to benzene or other valuable chemicals is a very promising process for the efficient application of natural gas. Compared with conversion processes that require oxidants, non-oxidative direct conversion is more attractive due to high selectivity to the target product. In this paper, an alternative route for methane dehydrogenation and selective conversion to benzene and hydrogen without the participation of oxygen is discussed. A brief review of the catalysts used in methane dehydroaromatization （MDA） is first given, followed by our current understanding of the location and the active phase of Mo species, the reaction mechanism, the mechanism of carbonaceous deposit and the deactivation of Mo/zeolite catalysts are systematically discussed. Ways to improve the catalytic activity and stability are described in detail based on catalyst and reaction as well as reactor design. Future prospects for methane dehydroaromatization process are also presented.
基金financially supported by the"Strategic Priority Research Program"of Chinese Academy of Sciences(No.XDA09030101)the National Natural Science Foundation of China(No.21103181 and 21473185)+1 种基金DICP Fundamental Research Program for Clean Energy(DICP M201301)Shaanxi Yanchang Petroleum Group Co.Ltd
文摘Long-term stability test of Mo/HZSM-5-N catalysts（HZSM-5-N stands for nano-sized HZSM-5） in methane dehydroaromatization（MDA）reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 1000 h.During this test,methane conversion ranges from 13% to 16%,and mean yield to aromatics（i.e.benzene and naphthalene） exceeds 10%.N2-physisorption,XRD,NMR and TPO measurements were performed for the used Mo/HZSM-5 catalysts and coke deposition,and the results revealed that the periodic hydrogenation can effectively suppress coke deposition by removing the inert aromatic-type coke,thus ensuring Mo/HZSM-5 partly maintained its activity even in the presence of large amount of coke deposition.The effect of zeolite particle size on the catalytic activity was also explored,and the results showed that the nano-sized zeolite with low diffusion resistance performed better.It is recognized that the size effect was enhanced by reaction time,and it became more remarkable in a long-term MDA reaction even at a low space velocity.
文摘Three industry-supplied, well-shaped Mo/HZSM-5 catalysts, two binder-added and one binder-free, were tested for the first time in methane dehydroaromatization to benzene at 1073 K and 10000 mL/（g·h） in periodic CH4-H2 switch operation mode, and their catalytic performances were compared with those of three self-prepared, binder-free powder Mo/HZSM-5 catalysts. XRD, 27Al NMR, SEM, BET and NH3-TPD characterizations of all the catalysts show that the zeolites in the two binder-added catalysts are comparable to those in the three binder-free powder catalysts in crystallinity, crystal size, micropore volume and Br{／o}nsted acidity. The test results, on the other hand, show that the catalytic performances of the two binder-added catalysts are worse than those of the four binder-free catalysts on both catalyst mass and zeolite mass bases. Then, TPO and BET measurements of all spent samples were conducted to get a deep insight into the negative effects of binder addition, and the results suggest that the binder additives functioned mainly to enhance the polyaromatization of formed aromatics to coke on their external surfaces and consequently lower the catalysts＇ benzene formation activity and selectivity.
基金supported by the Joint Studies Program (No. 18-502, and 19-501) of UVSOR-IMS, Japansupported by the Joint Studies Program (No. 2000G274, 2004G110)of KEK-PF, Japan
文摘For direct gas to liquid（GTL）,a novel process producing energy sources for methane dehydroaromatization is needed.Supporting MoO3 on H-MFI zeolite shows the high catalytic capacity and a selective activity for dehydroaromatization of methane to benzene at 973 K in a fixed bed reactor.On the other hand,deactivation by coke on the active sites in all the catalysts is formed during the reaction.H2 co-feed suppressed the deactivation,which is probably due to the decrease in coking amount.Mo K-edge X-ray absorption fine structure（XAFS） results showed the formation of dispersed Mo2C species with low crystallinity after dehydroaromatization.Mo LIII-edge XANES（X-ray absorption near-edge structure） indicated the formation of active Mo species including Mo2C and Mo-oxycarbide（MoOxCy）,where the redox state should be independent in the absence/presence of H2.It is concluded that Mo-oxycarbide species act as highly active species,and their stability affected the durable activity in the presence of H2.
基金supported by the National Basic Research Program of China (2005CB221400)x
文摘The promotion effect of CO in methane dehydroaromatization was investigated using ^13CO probe molecules. By alternative injection of ^13CO to the methane feed, the distribution of ^13CxC6-xH6（x= 0-3） products changed significantly, confirming the participation of ^13CO in the reaction network. The addition of ^13CO did not change the conversion of CH4 but improved slightly the durability of the methane dehydroaromatization （MDA） reaction, which might be caused by the interaction of the dissociated oxygen species and the deposited carbon species. The ratio of ^13CxC6-xH6 （x = 0-3） varied with the time on stream, which was determined by the competitive reactions of methane decomposition and ^13CO dissociation.
基金Financial supports from the Ministry of Science and Technology of Chinathe Natural Science Foundation of China+1 种基金the Chinese Academy of Sciencethe BP-China Joint Research Center are gratefully acknowledged.
文摘The effect of dimethyl ether (DME) co-feed on the catalytic performance of methane dehy-droaromatization (MDA) over 6Mo/HZSM-5 catalyst was investigated as a function of DME concentration under reaction conditions of T=1023 K, p=101 kPa and SV=1500 ml/(g·h). A high benzene yield was obtained and the stability of the catalyst was improved by adding 1.5%DME to the CH4 feed. The C6H6 yield was as high as ca. 10% even after reaction for 6 h. The stability of the catalyst was further improved when DME concentration in the co-feed gas was increased to an appropriate value. TGA and TPO results of the used 6Mo/HZSM-5 catalyst showed that the amount of coke on the used catalyst was reduced and the chemical nature of the coke was changed. When 1.5%DME was added to the CH4 feed, the coke formed on the catalyst could be burned off more easily than that when only CH4 was used as reactant. It is supposed that the oxygen in DME may play a role in preventing the coke burnt off at lower temperature from transforming into the coke burnt off at higher temperature, which results in the improvement of the stability of the catalyst.
基金financial support from the University of Tulsa (Faculty Development Summer Fellowship)ACS-PRF (PRF# 56052-DNI9) are gratefully acknowledged
文摘Methane dehydroaromatization was studied over Mo/SiO2 and Mo/HZSM-5 with different Mo loadings(2, 5, 10 wt%) at 973 K and 1023 K in a recirculating batch reactor. H2 pretreatment at 1023 K prior to methane activation has significantly improved the catalyst activity with increase in Mo loading and reduced the induction time on benzene formation in both Mo/SiO2 and Mo/HZSM-5. 10 wt% Mo/HZSM-5 gave a maximum methane conversion of 19% and ~67% benzene selectivity at 1023 K. The XRD analysis of used catalysts revealed that the Mo O3 species were converted to β-Mo2C phase. Studies on Mo/SiO2 catalysts showed that benzene was formed even in the absence of acidic zeolite sites. Reactions of ethylene in the presence of pure silica, HZSM-5 and in a blank reactor revealed that conversion of ethylene to aromatics was similar in case of the blank reactor and silica. Thus, it is believed that molybdenum carbide sites act as active sites only for C–H bond activation of methane and ethylene formation. Even though, ethylene can undergo subsequent oligomerization without any catalytic aid to form benzene at973 K and above addition of acidic zeolites improved the selectivity of benzene.
文摘The dehydroaramatization of methane over W-supported ZSM-5 with varying degrees of Li+ ion-exchanged catalysts was studied with and without oxygen at 1073 K and atmospheric pressure. Catalyst activity and stability were found to be influenced by the catalyst acidity related to Bronsted acid sites and by the presence of oxygen in the feed. The NH3-TPD and FTIR-pyridine results demonstrated that partially exchanged of H+ ions by Li+ into the W/HZSM-5 catalysts could be used to control the amount of strong acid sites on the catalyst surface. Without oxygen, the 3WHLi-Z (5:1) catalyst that has strong acid sites equal to nearly 74% of the original strong acid sites in the parent HZSM-5 exhibited the highest methane conversion and selectivity towards aromatics. However, the catalyst deactivated in a five hour period. In the presence of oxygen, the catalyst activity and stability could be improved further. The results of this study revealed that a suitable amount of strong Bronsted acid sites as well as oxygen addition in the feed increased the catalyst activity and stability. The 3WHLi-Z(5:1) catalyst exhibited improved performance in the dehydroaromatization of methane.
基金Financial support from CNPq, FINEP, PETROBRAS and FAPERJ.
文摘The effect of addition of Ru and Pd to Mo/HZSM-5 catalysts used in the dehydroaromatization of methane was investigated. Catalytic tests and temperature-programmed oxidation results showed that Pd-based catalysts were more selective to naphthalene and suffered strong deactivation. The presence of Ru improved the activity and stability, with a decrease in the carbonaceous deposit probably because of a mechanism of protection of the Mo2C surface.
基金Supported by Hydrocarbon High-efficiency Utilization Technology Research Center of Yanchang Petroleum(Group)Co.Ltd,China(Contract No.HCRC-C13-010)by the National Natural Science Foundation of China(21536009)
文摘A pilot-scale methane dehydroaromatization–H_2regeneration fluidized bed system(MDARS)was developed.In the MDARS,the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help of a catalyst feeder allowed methane dehydroaromatization(MDA)and H_2regeneration to be carried out simultaneously,which is good for maintaining a stable MDA catalytic activity.A fixed bed reactor(FB)and a single fluidized bed reactor(SFB)were also used for a comparative study.The experimental results showed that the catalytic activity in the MDARS was more stable than that in the FB and SFB reactors.The effects of some parameters of MDARS on the CH_4conversion and product selectivity were investigated.To verify the feasibility and reliability of the MDARS,an eight-hour long-term test was carried out,which demonstrated that the operation of the MDARS was stable and that the catalytic activity remained stable throughout the entire experimental period.
