An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 7...An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 717 resins based on the coordination difference between Zn^(2+)/Cu^(2+)and Cl^(-).The theoretical calculation and spectroscopic analyses suggested that the coordination between Zn^(2+)and Cl^(-)is much stronger than that between Cu^(2+)and Cl^(-),and the Cl-concentration significantly affects Zn(Ⅱ)and Cu(Ⅱ)species.The factors involving Cl-concentration,resin dosage,shaking speed,and temperature were investigated to determine the optimal condition,and the maximum separation factor of Zn/Cu reached as high as 479.2.The results of the adsorption isotherms,adsorption kinetics,SEM,FTIR,and XPS analyses indicated that the process followed the monolayer uniform chemisorption.Through the continuous adsorption experiments,Zn(Ⅱ)and Cu(Ⅱ)in the high-chlorine raffinate were separately recovered,allowing the reuse of residual waste acid and germanium.展开更多
Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemi...Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemical industry.In this paper,a dual metal catalysis system combining a Ru-isomerization catalyst and a Rh-linear-hydroformylation catalyst satisfying the“4S”criterions was reported for isomerization-linear-hydroformylation of C4 raffinate(mixed butenes)and internal olefins.The optimized dual metal catalyst system hydroformylated Raffinate II feed to valuable valeraldehyde in 98%linear selectivity(n:i=49),80%conversion and high activity of 1069 h^(−1)TOF whereas 96%linear selectivity(n:i=24),71%conversion and 948 h^(−1)TOF were observed using only the Rh-hydroformylation catalyst.Notably,valeraldehyde are produced in million tons scale annually for making non-toxic plasticizer DPHP.Various 2-olefins were also converted to linear aldehydes in>98%linear selectivity(n:i>49),78%-82%conversion and high activity of 802-851 h^(−1)TOF.展开更多
基金financially supported by the Postdoctoral Research Foundation of Central South University,China(No.140050037)。
文摘An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 717 resins based on the coordination difference between Zn^(2+)/Cu^(2+)and Cl^(-).The theoretical calculation and spectroscopic analyses suggested that the coordination between Zn^(2+)and Cl^(-)is much stronger than that between Cu^(2+)and Cl^(-),and the Cl-concentration significantly affects Zn(Ⅱ)and Cu(Ⅱ)species.The factors involving Cl-concentration,resin dosage,shaking speed,and temperature were investigated to determine the optimal condition,and the maximum separation factor of Zn/Cu reached as high as 479.2.The results of the adsorption isotherms,adsorption kinetics,SEM,FTIR,and XPS analyses indicated that the process followed the monolayer uniform chemisorption.Through the continuous adsorption experiments,Zn(Ⅱ)and Cu(Ⅱ)in the high-chlorine raffinate were separately recovered,allowing the reuse of residual waste acid and germanium.
基金R.Zhang gratefully acknowledges the Free Exploration Fund from the Science and Technology Innovation Committee of Shenzhen(No.JCYJ20170817104824122)We are grateful for the financial support from the National Natural Science Foundation of China(No.22001113)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemical industry.In this paper,a dual metal catalysis system combining a Ru-isomerization catalyst and a Rh-linear-hydroformylation catalyst satisfying the“4S”criterions was reported for isomerization-linear-hydroformylation of C4 raffinate(mixed butenes)and internal olefins.The optimized dual metal catalyst system hydroformylated Raffinate II feed to valuable valeraldehyde in 98%linear selectivity(n:i=49),80%conversion and high activity of 1069 h^(−1)TOF whereas 96%linear selectivity(n:i=24),71%conversion and 948 h^(−1)TOF were observed using only the Rh-hydroformylation catalyst.Notably,valeraldehyde are produced in million tons scale annually for making non-toxic plasticizer DPHP.Various 2-olefins were also converted to linear aldehydes in>98%linear selectivity(n:i>49),78%-82%conversion and high activity of 802-851 h^(−1)TOF.