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
Identification of the catalyst characteristics correlating with the key performance parameters including selectivity and stability is key to the rational catalyst design. Herein we focused on the identification of pro...Identification of the catalyst characteristics correlating with the key performance parameters including selectivity and stability is key to the rational catalyst design. Herein we focused on the identification of property-performance relationships in the methanol-to-olefin(MTO) process by studying in detail the catalytic behaviour of MFI, MEL and their respective intergrowth zeolites. The detailed material characterization reveals that both the high production of propylene and butylenes and the large Me OH conversion capacity correlate with the enrichment of lattice Al sites in the channels of the pentasil structure as identified by 27 Al MAS NMR and 3-methylpentane cracking results. The lack of correlation between MTO performance and other catalyst characteristics, such as crystal size, presence of external Brønsted acid sites and Al pairing suggests their less pronounced role in defining the propylene selectivity. Our analysis reveals that catalyst deactivation is rather complex and is strongly affected by the enrichment of lattice Al in the intersections, the overall Al-content, and crystal size. The intergrowth of MFI and MEL phases accelerates the catalyst deactivation rate.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
Sulfonated lignin has potential applications in various fields,including wastewater treatment,the textile industry,and construction.Although the reaction chemistry of sulfonated lignin has been well studied,the method...Sulfonated lignin has potential applications in various fields,including wastewater treatment,the textile industry,and construction.Although the reaction chemistry of sulfonated lignin has been well studied,the method of drying this material after synthesis has not been evaluated.In this study,sulfoethylated kraft lignin(SEKL)was synthesized as a representative sulfonated lignin to investigate the impact of drying temperature on its structure and properties.For SEKL,freeze-drying at-55℃ resulted in the highest charge density,water-solubility,and more uniform chemical structures.The sulfonic acid groups underwent alkylation reaction after the sample was oven-dried at 55 and 80℃,which was accompanied by a reduction in solubility and charge den-sity of the sample,as well as an increase in glass transition temperature.Furthermore,the sample after drying at higher temperatures of 105 and 130℃ not only exhibited the alkylation but also underwent hydrolysis of the sulfonic acid groups at the phenolic position of lignin.This change was accompanied by a further reduction in molecular weight,solubility,and charge density,as well as a decrease in the glass transition temperature.It was found that the alkylation and hydrol-ysis of SEKL occurred to varying degrees,and higher temperatures promoted hydrolysis.Based on the results of this work,drying temperature has a significant effect on the properties of the SEKL sample,implying that it must be taken into account when considering its application in different fields.展开更多
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 BASF and the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC) for Funding under Project (2016.007.TUD)
文摘Identification of the catalyst characteristics correlating with the key performance parameters including selectivity and stability is key to the rational catalyst design. Herein we focused on the identification of property-performance relationships in the methanol-to-olefin(MTO) process by studying in detail the catalytic behaviour of MFI, MEL and their respective intergrowth zeolites. The detailed material characterization reveals that both the high production of propylene and butylenes and the large Me OH conversion capacity correlate with the enrichment of lattice Al sites in the channels of the pentasil structure as identified by 27 Al MAS NMR and 3-methylpentane cracking results. The lack of correlation between MTO performance and other catalyst characteristics, such as crystal size, presence of external Brønsted acid sites and Al pairing suggests their less pronounced role in defining the propylene selectivity. Our analysis reveals that catalyst deactivation is rather complex and is strongly affected by the enrichment of lattice Al in the intersections, the overall Al-content, and crystal size. The intergrowth of MFI and MEL phases accelerates the catalyst deactivation rate.
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.
基金supported by the NSERC(No.2024-06194),Canada Research Chairs(No.950-230466)Northern Ontario Heritage Fund Corporation programs(No.8320002).
文摘Sulfonated lignin has potential applications in various fields,including wastewater treatment,the textile industry,and construction.Although the reaction chemistry of sulfonated lignin has been well studied,the method of drying this material after synthesis has not been evaluated.In this study,sulfoethylated kraft lignin(SEKL)was synthesized as a representative sulfonated lignin to investigate the impact of drying temperature on its structure and properties.For SEKL,freeze-drying at-55℃ resulted in the highest charge density,water-solubility,and more uniform chemical structures.The sulfonic acid groups underwent alkylation reaction after the sample was oven-dried at 55 and 80℃,which was accompanied by a reduction in solubility and charge den-sity of the sample,as well as an increase in glass transition temperature.Furthermore,the sample after drying at higher temperatures of 105 and 130℃ not only exhibited the alkylation but also underwent hydrolysis of the sulfonic acid groups at the phenolic position of lignin.This change was accompanied by a further reduction in molecular weight,solubility,and charge density,as well as a decrease in the glass transition temperature.It was found that the alkylation and hydrol-ysis of SEKL occurred to varying degrees,and higher temperatures promoted hydrolysis.Based on the results of this work,drying temperature has a significant effect on the properties of the SEKL sample,implying that it must be taken into account when considering its application in different fields.
