随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO...随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.展开更多
Aromatics are important basic chemicals. However, direct conversion of syngas via the conventional Fischer-Tropsch synthesis produces little aromatics. We presented herein that a bifunctional composite of ZSM-5 in com...Aromatics are important basic chemicals. However, direct conversion of syngas via the conventional Fischer-Tropsch synthesis produces little aromatics. We presented herein that a bifunctional composite of ZSM-5 in combination with Zn Cr Oxcatalyzes syngas conversion to aromatics. Particularly, ZSM-5 crystals with a sheet-like morphology can enhance significantly the aromatization activity. The lower length ratio of the b/a axes of the crystals, the more aromatics form but without influencing the selectivity of small molecules such as CH4 and C2–C4. Since the acid properties and the Al chemical environment were not altered while the morphology changed, the enhanced aromatic selectivity is likely attributed to the favored diffusion of aromatics in these sheet-like crystals.展开更多
Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and ...Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.展开更多
Sulfated porous carbon （PC-SO3H） catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-...Sulfated porous carbon （PC-SO3H） catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-hydroxymethylfurfural from fructose.展开更多
Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
In the interlayer expansion of the layered zeolite precursor COK-5, a Sn, salt, bis（2,4-pentanedionate）- dichlorotin [Sn（acac）2CL2], instead of a silylating agent was used to link the layers at 180 ℃. The obtaine...In the interlayer expansion of the layered zeolite precursor COK-5, a Sn, salt, bis（2,4-pentanedionate）- dichlorotin [Sn（acac）2CL2], instead of a silylating agent was used to link the layers at 180 ℃. The obtained material, which is designed as Sn-COE-5, shows a shift of the first XRD reflection, which is very similar to that of COK-5 interlayer expanded with dichlorodimethylsilane （DCDMS）, indicating an increase in interlayer distance. X-ray diffraction （XRD）, N2 sorption isotherms, inductively coupled plasma （ICP）, and X-ray photo- electron spectroscopy （XPS） support the incorporation of isolated Sn sites in the sample. In the conversion of glucose to levulinic acid. Sn-COE-5 exhibits much higher activity than COK-5, which is due to the presence of Lewis acidic sites in the Sn-COE-5.展开更多
Diesel vehicles have caused serious environmental problems in China.Hence,the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in...Diesel vehicles have caused serious environmental problems in China.Hence,the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in the latest China VI standard.To fulfill this stringent legislation,two major technical routes,including the exhaust gas recirculation(EGR)and high-efficiency selective catalytic reduction(SCR)routes,have been developed for diesel engines.Moreover,complicated aftertreatment technologies have also been developed,including use of a diesel oxidation catalyst(DOC)for controlling carbon monoxide(CO)and hydrocarbon(HC)emissions,diesel particulate filter(DPF)for particle mass(PM)emission control,SCR for the control of NOx emission,and an ammonia slip catalyst(ASC)for the control of unreacted NH3.Due to the stringent requirements of the China VI standard,the aftertreatment system needs to be more deeply integrated with the engine system.In the future,aftertreatment technologies will need further upgrades to fulfill the requirements of the near-zero emission target for diesel vehicles.展开更多
The most used method for preparation of zeolites is hydrothermal synthesis from silicate or aluminosilicate gels at temperatures in the range of 60–200°C.Excess water used in the industrial process results in se...The most used method for preparation of zeolites is hydrothermal synthesis from silicate or aluminosilicate gels at temperatures in the range of 60–200°C.Excess water used in the industrial process results in several issues,including high autogeneous pressure,low efficiency,pollution,etc.To solve these problems,several strategies have been developed.This review describes the solvent-free synthesis of zeolites.The combination of solvent-free synthesis and organotemplate-free synthesis can open the pathway to a highly sustainable zeolite synthesis protocol in industry.展开更多
Zeolites have been regarded as one of the most important catalysts in petrochemical industry due to their excellent catalytic performance. However, the sole micro- pores in zeolites severely limit their applications i...Zeolites have been regarded as one of the most important catalysts in petrochemical industry due to their excellent catalytic performance. However, the sole micro- pores in zeolites severely limit their applications in oil refining and natural gas conversion. To solve the problem, mesoporous zeolites have been prepared by introducing mesopores into the zeolite crystals in recent years, and thus have the advantages of both mesostructured materials （fast diffusion and accessible for bulky molecules） and micro- porous zeolite crystals （strong acidity and high hydro- thermal stability）. In this review, after giving a brief introduction to preparation, structure, and characterization of mesoporous zeolites, we systematically summarize catalytic applications of these mesoporous zeolites as efficient catalysts in oil refining and natural gas conversion including catalytic cracking of heavy oil, alkylation, isomerization, hydrogenation, hydrodesulfurization, methane dehydroaromatization, methanol dehydration to dimethyl ether, methanol to olefins, and methanol to hydrocarbons.展开更多
SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 ze...SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 zeolite catalyst.One solution for this challenge is to introduce mesoporosity in the SSZ-39 zeolite.Herein,we report the synthesis of mesoporous SSZ-39 zeolite using an organosilane surfactant,,-dimethyl--(3-(trimethoxysilyl)propyl)octan-1-aminium chloride,as a mesopore template and,-dimethyl--2,6-dimethylpiperidinium as a micropore template.The obtained zeolites were characterized by X-ray diffraction,N sorption,scanning electron microscopy,temperature programmed desorption of ammonia,and magic angle spinning nuclear magnetic resonance of Al.The results show that the mesoporous SSZ-39 zeolite has high crystallinity,meso/microporosity,high surface area,cuboid morphology,and abundant acidic sites.More importantly,this mesoporous SSZ-39 zeolite exhibits enhanced catalyst lifetime in the MTO reaction due to the presence of mesoporosity for fast mass transfer,compared with a conventional SSZ-39 zeolite without mesoporosity.展开更多
Development of the sustainable routes for synthesis of ITQ-family zeolites is very important because of their unique structures and excellent catalytic and adsorptive properties.The burden of costly raw materials and ...Development of the sustainable routes for synthesis of ITQ-family zeolites is very important because of their unique structures and excellent catalytic and adsorptive properties.The burden of costly raw materials and low efficiency of synthesis put a strong challenge for their widespread commercial application.Here,we show an alternative and simple route for synthesis of ITQ-12,ITQ-13,and ITQ-17 zeolites using commercially available organic templates by a facile grinding process of anhydrous starting raw solids,followed by heating at 140-180 ℃.Compared with the conventional hydrothermal synthesis,this approach has obvious advantages such as employment of low-cost organic templates with very high effectiveness,high yield of zeolite products,short crystallization time,and relatively simple procedures.This methodology might open a pathway to synthesize ITQ zeolites with more sustainable manner.展开更多
Recovery and purify of light olefins from the off-gas ofthe catalytic crackers have been focused for more than50 years, driven largely by the escalating demand forfeedstock for production of polyethylene and poly-prop...Recovery and purify of light olefins from the off-gas ofthe catalytic crackers have been focused for more than50 years, driven largely by the escalating demand forfeedstock for production of polyethylene and poly-propylene, which requires the separation of C2H4/C2H6and C3H6/C3H8 mixtures in which the olefins and paraf-fins are present at roughly equal concentrations [1,2].展开更多
文摘随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.
基金supported by the National Key R&D Program of China(2017YFB0702800)the National Natural Science Foundation of China(2152780065,91634201 and 21720102001)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)~~
基金supported by the National Natural Science Foundation of China(91545111,91634201,21720102001)National Key Research and Development Program of China(2017YFB0702803)Shell Foundation~~
基金financially supported by the Ministry of Science and Technology of China(no.2017YFB0602201)the National Natural Science Foundation of China(Grant no.21425312,91645204 and 21621063)
文摘Aromatics are important basic chemicals. However, direct conversion of syngas via the conventional Fischer-Tropsch synthesis produces little aromatics. We presented herein that a bifunctional composite of ZSM-5 in combination with Zn Cr Oxcatalyzes syngas conversion to aromatics. Particularly, ZSM-5 crystals with a sheet-like morphology can enhance significantly the aromatization activity. The lower length ratio of the b/a axes of the crystals, the more aromatics form but without influencing the selectivity of small molecules such as CH4 and C2–C4. Since the acid properties and the Al chemical environment were not altered while the morphology changed, the enhanced aromatic selectivity is likely attributed to the favored diffusion of aromatics in these sheet-like crystals.
基金supported by the Ministry of Science and Technology of China (No.2017YFB0602201)the Chinese Academy of Sciences (XDA21020400)+2 种基金the National Natural Science Foundation of China (Grant nos.91645204, 21425312 and 21621063)the Youth Innovation Promotion Association of Chinese Academy of Sciences (2019184)the INCOE (International Network of Centers of Excellence) project coordinated by BASF SE
文摘Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.
基金supported by the National Natural Science Foundation of China (U1162201)the Graduate Innovation Fund of Jilin University (20121051)
文摘Sulfated porous carbon （PC-SO3H） catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-hydroxymethylfurfural from fructose.
基金the National Natural Science Foundation of China(20973079 and U1162201)Graduate Innovation Fund of Jilin University(20121051)
文摘Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
基金supported by the National Natural Science Foundation of China (21422306 and 21403192)Zhejiang Provincial Natural Science Foundation of China under grant no. LR15B030001the Fundamental Research Funds for the Central Universities (2015XZZX004-04)
文摘In the interlayer expansion of the layered zeolite precursor COK-5, a Sn, salt, bis（2,4-pentanedionate）- dichlorotin [Sn（acac）2CL2], instead of a silylating agent was used to link the layers at 180 ℃. The obtained material, which is designed as Sn-COE-5, shows a shift of the first XRD reflection, which is very similar to that of COK-5 interlayer expanded with dichlorodimethylsilane （DCDMS）, indicating an increase in interlayer distance. X-ray diffraction （XRD）, N2 sorption isotherms, inductively coupled plasma （ICP）, and X-ray photo- electron spectroscopy （XPS） support the incorporation of isolated Sn sites in the sample. In the conversion of glucose to levulinic acid. Sn-COE-5 exhibits much higher activity than COK-5, which is due to the presence of Lewis acidic sites in the Sn-COE-5.
基金supported by the National Key R&D Program of China(No.2017YFC0211101)the Key Project of National Natural Science Foundation(No.21637005)+1 种基金the Cultivating Project of Strategic Priority Research Program of Chinese Academy of Sciences(No.XDPB1902)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA23010200)。
文摘Diesel vehicles have caused serious environmental problems in China.Hence,the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in the latest China VI standard.To fulfill this stringent legislation,two major technical routes,including the exhaust gas recirculation(EGR)and high-efficiency selective catalytic reduction(SCR)routes,have been developed for diesel engines.Moreover,complicated aftertreatment technologies have also been developed,including use of a diesel oxidation catalyst(DOC)for controlling carbon monoxide(CO)and hydrocarbon(HC)emissions,diesel particulate filter(DPF)for particle mass(PM)emission control,SCR for the control of NOx emission,and an ammonia slip catalyst(ASC)for the control of unreacted NH3.Due to the stringent requirements of the China VI standard,the aftertreatment system needs to be more deeply integrated with the engine system.In the future,aftertreatment technologies will need further upgrades to fulfill the requirements of the near-zero emission target for diesel vehicles.
基金supported by the National Natural Science Foundation of China(21273197,21333009,21203165)Fundamental Research Funds for the Central Universities(2013XZZX001)+1 种基金the National High Technology Research and Development Program of China(2013AA065301)the Science and Technology Innovative Team of Zhejiang Province(2012R10014-02)
文摘The most used method for preparation of zeolites is hydrothermal synthesis from silicate or aluminosilicate gels at temperatures in the range of 60–200°C.Excess water used in the industrial process results in several issues,including high autogeneous pressure,low efficiency,pollution,etc.To solve these problems,several strategies have been developed.This review describes the solvent-free synthesis of zeolites.The combination of solvent-free synthesis and organotemplate-free synthesis can open the pathway to a highly sustainable zeolite synthesis protocol in industry.
文摘Zeolites have been regarded as one of the most important catalysts in petrochemical industry due to their excellent catalytic performance. However, the sole micro- pores in zeolites severely limit their applications in oil refining and natural gas conversion. To solve the problem, mesoporous zeolites have been prepared by introducing mesopores into the zeolite crystals in recent years, and thus have the advantages of both mesostructured materials （fast diffusion and accessible for bulky molecules） and micro- porous zeolite crystals （strong acidity and high hydro- thermal stability）. In this review, after giving a brief introduction to preparation, structure, and characterization of mesoporous zeolites, we systematically summarize catalytic applications of these mesoporous zeolites as efficient catalysts in oil refining and natural gas conversion including catalytic cracking of heavy oil, alkylation, isomerization, hydrogenation, hydrodesulfurization, methane dehydroaromatization, methanol dehydration to dimethyl ether, methanol to olefins, and methanol to hydrocarbons.
基金the National Key Research and Development Program of China(Grant No.2017YFC0211101)the National Natural Science Foundation of China(Grant Nos.21333009,21703203 and 21673205).
文摘SSZ-39 zeolite with AEI framework structure is a good catalyst candidate for the methanol-to-olefins(MTO)reaction.However,the diffusion limitation and coke formation often results in fast deactivation of the SSZ-39 zeolite catalyst.One solution for this challenge is to introduce mesoporosity in the SSZ-39 zeolite.Herein,we report the synthesis of mesoporous SSZ-39 zeolite using an organosilane surfactant,,-dimethyl--(3-(trimethoxysilyl)propyl)octan-1-aminium chloride,as a mesopore template and,-dimethyl--2,6-dimethylpiperidinium as a micropore template.The obtained zeolites were characterized by X-ray diffraction,N sorption,scanning electron microscopy,temperature programmed desorption of ammonia,and magic angle spinning nuclear magnetic resonance of Al.The results show that the mesoporous SSZ-39 zeolite has high crystallinity,meso/microporosity,high surface area,cuboid morphology,and abundant acidic sites.More importantly,this mesoporous SSZ-39 zeolite exhibits enhanced catalyst lifetime in the MTO reaction due to the presence of mesoporosity for fast mass transfer,compared with a conventional SSZ-39 zeolite without mesoporosity.
文摘Development of the sustainable routes for synthesis of ITQ-family zeolites is very important because of their unique structures and excellent catalytic and adsorptive properties.The burden of costly raw materials and low efficiency of synthesis put a strong challenge for their widespread commercial application.Here,we show an alternative and simple route for synthesis of ITQ-12,ITQ-13,and ITQ-17 zeolites using commercially available organic templates by a facile grinding process of anhydrous starting raw solids,followed by heating at 140-180 ℃.Compared with the conventional hydrothermal synthesis,this approach has obvious advantages such as employment of low-cost organic templates with very high effectiveness,high yield of zeolite products,short crystallization time,and relatively simple procedures.This methodology might open a pathway to synthesize ITQ zeolites with more sustainable manner.
文摘Recovery and purify of light olefins from the off-gas ofthe catalytic crackers have been focused for more than50 years, driven largely by the escalating demand forfeedstock for production of polyethylene and poly-propylene, which requires the separation of C2H4/C2H6and C3H6/C3H8 mixtures in which the olefins and paraf-fins are present at roughly equal concentrations [1,2].
