Dividing wall column(DWC)is shown to be energy efficient compared to conventional column sequence for multi components separation,which is used for olefin separation in fluidization methanol to propylene process in th...Dividing wall column(DWC)is shown to be energy efficient compared to conventional column sequence for multi components separation,which is used for olefin separation in fluidization methanol to propylene process in the present work.Detailed design for pilot DWC was performed and five control structures,i.e.composition control(CC),temperature control(TC),composition-temperature control(CC-TC),temperature difference control(TDC),double temperature difference control(DTDC)were proposed to circumvent feed disturbance.Sensitivity analysis and singular value decomposition(SVD)were used as criterion to select the controlled temperature locations in TC,CC-TC,TDC and DTDC control loops.The steady simulation result demonstrates that 25.7% and 30.2% duty can be saved for condenser and reboiler by substituting conventional column sequence with DWC,respectively.As for control structure selection,TC and TDC perform better than other three control schemes with smaller maximum deviation and shorter settling time.展开更多
With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))fro...With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.展开更多
Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, ...Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, on cooling to room temperature, the catalyst could precipitate out from organic phase and was easily separated by decantation and reused six times without obvious decreasing in activity.展开更多
Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive...Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.展开更多
Halogenated alkanes are high-value chemical feedstocks in synthetic chemistry and petrochemical industry[1,2].Therefore,the separation of halogenated alkane isomers is one of the necessary chemical processes in the pe...Halogenated alkanes are high-value chemical feedstocks in synthetic chemistry and petrochemical industry[1,2].Therefore,the separation of halogenated alkane isomers is one of the necessary chemical processes in the petrochemical industry.However,the isomers normally have close boiling points due to the same molecular weight and similar chemical structure,which makes it difficult to separate the isomers with high purity by traditional methods such as distillation.Consequently,it is of great significance for petrochemical industry to find an efficient and energy-saving scheme to separate halogenated alkanes isomers.展开更多
The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-solubl...The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-soluble cavitand host for guests that are hydro-phobic and have narrow or flat shapes.The host showed selectivity for trans 1,4-dimethylcyclohexane over the cis-isomers.The sep-arations of n-alkanes from isooctane by gas/liquid adsorption and a liquid/liquid extraction are detailed.展开更多
Chemical complexation, in which certain metal ions （especially Ag^＋ and Cu^＋） reversibly and selectively complex olefin isomers, was used to separate 1-hexene from a mixture of internal hexenes as an attractive al...Chemical complexation, in which certain metal ions （especially Ag^＋ and Cu^＋） reversibly and selectively complex olefin isomers, was used to separate 1-hexene from a mixture of internal hexenes as an attractive alternative to traditional distillation. Several potential reactive extractants were investigated for their selectivity of both 1-hexene to 2-hexene and 1-hexene to 3-hexene. With 3 mol/L AgNO3-N-methyl-pyrrolidone （NMP） solution as extractant, the selectivity of 1-hexene to 3-hexane was increased to about 2.0 and the selectivity of 1-hexene to 2-hexene reached 1.5. Both the raffinate phase and the extracted phase were analyzed using a gas chromatograph equipped with a flame ionization detector and a 50-m capillary column. The experimental results show that the silver nitrate NMP solution has the better selectivity than other reactive extractions.展开更多
C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points...C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points.Here,we for the first time employ two anionpillared hybrid porous materials(ZU-62 and TIFSIX-2-Cu-i)towards the challenging separation of C5 olefin mixtures(trans-2-pentene,1-pentene and isoprene).These two adsorbents not only exhibit the unprecedented separation performance,but also show excellent recycle performance.Owing to the favorable electrostatic environment within a suitable confined space,TIFSIX-2-Cu-i is able to distinguish the three C5 olefins(frans-2-pentene,1-pentene and isoprene)with a high uptake of trans-2-pentene(3.1mmgol·g^(-1))ZU-62(also termed as NbOFFIVE-2-Cu-i)with contracted aperture size shows exclusion effect to the relatively large molecule of isoprene at low pressure range(0-6 kPa),contributing to the excellent separation selectivity of 1-pentene/isoprene(300).The excellent separation performance of ZU-62 and TIFSIX-2-Cu-i is verified by the breakthrough experiment.And interestingly,the regeneration tests show that C5 olefins can be easily desorbed from ZU-62,TIFSIX-2-Cu-i under 298 K.Moreover,the detailed adsorption behavior is further revealed by simulation studies.展开更多
基金Supported by Open Research Project of State Key Laboratory of Chemical Engineering(Grant No.SKL-Ch E-16B06)
文摘Dividing wall column(DWC)is shown to be energy efficient compared to conventional column sequence for multi components separation,which is used for olefin separation in fluidization methanol to propylene process in the present work.Detailed design for pilot DWC was performed and five control structures,i.e.composition control(CC),temperature control(TC),composition-temperature control(CC-TC),temperature difference control(TDC),double temperature difference control(DTDC)were proposed to circumvent feed disturbance.Sensitivity analysis and singular value decomposition(SVD)were used as criterion to select the controlled temperature locations in TC,CC-TC,TDC and DTDC control loops.The steady simulation result demonstrates that 25.7% and 30.2% duty can be saved for condenser and reboiler by substituting conventional column sequence with DWC,respectively.As for control structure selection,TC and TDC perform better than other three control schemes with smaller maximum deviation and shorter settling time.
基金supported by Natural Science Foundation of Zhejiang Province(LR20B060001 and LZ18B060001)the National Natural Science Foundation of China(21725603,21938011),the Entrepreneur Team Introduction Program of Zhejiang(2019R01006)the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.
文摘With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29906001)and the Research Institute of Petroleum Processing.
文摘Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, on cooling to room temperature, the catalyst could precipitate out from organic phase and was easily separated by decantation and reused six times without obvious decreasing in activity.
文摘Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.
文摘Halogenated alkanes are high-value chemical feedstocks in synthetic chemistry and petrochemical industry[1,2].Therefore,the separation of halogenated alkane isomers is one of the necessary chemical processes in the petrochemical industry.However,the isomers normally have close boiling points due to the same molecular weight and similar chemical structure,which makes it difficult to separate the isomers with high purity by traditional methods such as distillation.Consequently,it is of great significance for petrochemical industry to find an efficient and energy-saving scheme to separate halogenated alkanes isomers.
基金the National Natural Science Foundation of China(Nos.21801164 and 22071144)Shanghai University(N.13-G210-20-201).Dr.Yang Yu thanks the Program for Professor of Special Appointment(Dongfang Scholarship)of the Shanghai Education Committee.
文摘The use of a metallo cavitand for the selective sequestration of n-alkanes from their mixtures with isooctane is described.Competition experiments and NMR spectroscopy are used to show the preference of a water-soluble cavitand host for guests that are hydro-phobic and have narrow or flat shapes.The host showed selectivity for trans 1,4-dimethylcyclohexane over the cis-isomers.The sep-arations of n-alkanes from isooctane by gas/liquid adsorption and a liquid/liquid extraction are detailed.
文摘Chemical complexation, in which certain metal ions （especially Ag^＋ and Cu^＋） reversibly and selectively complex olefin isomers, was used to separate 1-hexene from a mixture of internal hexenes as an attractive alternative to traditional distillation. Several potential reactive extractants were investigated for their selectivity of both 1-hexene to 2-hexene and 1-hexene to 3-hexene. With 3 mol/L AgNO3-N-methyl-pyrrolidone （NMP） solution as extractant, the selectivity of 1-hexene to 3-hexane was increased to about 2.0 and the selectivity of 1-hexene to 2-hexene reached 1.5. Both the raffinate phase and the extracted phase were analyzed using a gas chromatograph equipped with a flame ionization detector and a 50-m capillary column. The experimental results show that the silver nitrate NMP solution has the better selectivity than other reactive extractions.
基金the Zhejiang Provincial Natural Science Foundation of China(No.LR20B060001)the Key Research and Development Program of Ningxia(No.2018BDE02057)+1 种基金the National Natural Science Foundation of China(No.U1862110,21938011)Zhejiang University Academic Award for Out-standing Doctoral Candidates,and the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.The single-crystal X-ray diffraction data of TIFSIX-2-Cu-i have been deposited in the Cambridge Crystallographic Data Centre under accession num ber CCDC:1857691.
文摘C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points.Here,we for the first time employ two anionpillared hybrid porous materials(ZU-62 and TIFSIX-2-Cu-i)towards the challenging separation of C5 olefin mixtures(trans-2-pentene,1-pentene and isoprene).These two adsorbents not only exhibit the unprecedented separation performance,but also show excellent recycle performance.Owing to the favorable electrostatic environment within a suitable confined space,TIFSIX-2-Cu-i is able to distinguish the three C5 olefins(frans-2-pentene,1-pentene and isoprene)with a high uptake of trans-2-pentene(3.1mmgol·g^(-1))ZU-62(also termed as NbOFFIVE-2-Cu-i)with contracted aperture size shows exclusion effect to the relatively large molecule of isoprene at low pressure range(0-6 kPa),contributing to the excellent separation selectivity of 1-pentene/isoprene(300).The excellent separation performance of ZU-62 and TIFSIX-2-Cu-i is verified by the breakthrough experiment.And interestingly,the regeneration tests show that C5 olefins can be easily desorbed from ZU-62,TIFSIX-2-Cu-i under 298 K.Moreover,the detailed adsorption behavior is further revealed by simulation studies.
