The separation of hexane isomers is of vital importance to produce high quality gasoline in the petrochemical industry.However,the similar vapor pressure and boiling point of hexane isomers bring great difficulties an...The separation of hexane isomers is of vital importance to produce high quality gasoline in the petrochemical industry.However,the similar vapor pressure and boiling point of hexane isomers bring great difficulties and challenges in the separation process.Sieving effect,which allowing smaller molecules pass through and preventing others,should be a powerful strategy to solve this problem by making good use of porous materials.Therefore,physical separation by metal-organic framework(MOF)materials appears and becomes a burgeoning separation technique in industry.Due to the weak interaction between hexane isomers with absorbents,it puts forward higher requirements for the accurate design of MOF materials with optimal pore system.To address this issue,a novel MOF[Zn_(9)(tba)_(9)(dabco)_(3)]·12DMA-6MeOH(abbreviation:Zn_(9)(tba)_(9)(dabco)_(3);H_(2)tba=4-(1H-tetrazol-5-yl)-benzoic acid;dabco=1,4-diazabicyclo[2.2.2]octane;DMA=N,N-dimethylacetamide)with bcu network has been designed and synthesized by reticular chemistry strategy.Benefiting from the pre-designed topology and suitable linear ligand H_(2)tba and dabco,the structure of Zn_(9)(tba)_(9)(dabco)_(3)exhibits two types of channels with triangular-like and quadrilateral-like geometry.Zn_(9)(tba)_(9)(dabco)_(3)with appropriate channel size and shape displays potential selective adsorption capacity of vapor-phase hexane isomers through sieving effect.Moreover,outstanding gas adsorptive separation properties of Zn_(9)(tba)_(9)(dabco)_(3)could also be speculated by theoretical ideal adsorbed solution theory(IAST),suggesting Zn_(9)(tba)_(9)(dabco)_(3)can be regarded as a potential adsorbent material for purification natural gas_Breakthrough experiments show that Zn_(9)(tba)_(9)(dabco)_(3)is capable of discriminating all four hexane isomers at 298 K,and the corresponding research octane number(RON)of the eluted mixture closes to 95,which is higher than the standard for industrially refined hexane blends(about 83).We speculate that sieving effect and diffusion are a synergetic contributory factor in their elution dynamics,which may be ascribed to temperature-dependent interaction between pore aperture and each isomer.This work presents a typical example for design of efficient MOF absorbents by reticular chemistry strategy.展开更多
基金the National Natural Science Foundation of China(Nos.21771078,21621001)the 111 Project(No.B17020)+1 种基金the National Key Research and Development Program of China(No.2016YFB0701100)Zhejiang Provincial Natural Science Foundation of China(No.LQ18B010002).
文摘The separation of hexane isomers is of vital importance to produce high quality gasoline in the petrochemical industry.However,the similar vapor pressure and boiling point of hexane isomers bring great difficulties and challenges in the separation process.Sieving effect,which allowing smaller molecules pass through and preventing others,should be a powerful strategy to solve this problem by making good use of porous materials.Therefore,physical separation by metal-organic framework(MOF)materials appears and becomes a burgeoning separation technique in industry.Due to the weak interaction between hexane isomers with absorbents,it puts forward higher requirements for the accurate design of MOF materials with optimal pore system.To address this issue,a novel MOF[Zn_(9)(tba)_(9)(dabco)_(3)]·12DMA-6MeOH(abbreviation:Zn_(9)(tba)_(9)(dabco)_(3);H_(2)tba=4-(1H-tetrazol-5-yl)-benzoic acid;dabco=1,4-diazabicyclo[2.2.2]octane;DMA=N,N-dimethylacetamide)with bcu network has been designed and synthesized by reticular chemistry strategy.Benefiting from the pre-designed topology and suitable linear ligand H_(2)tba and dabco,the structure of Zn_(9)(tba)_(9)(dabco)_(3)exhibits two types of channels with triangular-like and quadrilateral-like geometry.Zn_(9)(tba)_(9)(dabco)_(3)with appropriate channel size and shape displays potential selective adsorption capacity of vapor-phase hexane isomers through sieving effect.Moreover,outstanding gas adsorptive separation properties of Zn_(9)(tba)_(9)(dabco)_(3)could also be speculated by theoretical ideal adsorbed solution theory(IAST),suggesting Zn_(9)(tba)_(9)(dabco)_(3)can be regarded as a potential adsorbent material for purification natural gas_Breakthrough experiments show that Zn_(9)(tba)_(9)(dabco)_(3)is capable of discriminating all four hexane isomers at 298 K,and the corresponding research octane number(RON)of the eluted mixture closes to 95,which is higher than the standard for industrially refined hexane blends(about 83).We speculate that sieving effect and diffusion are a synergetic contributory factor in their elution dynamics,which may be ascribed to temperature-dependent interaction between pore aperture and each isomer.This work presents a typical example for design of efficient MOF absorbents by reticular chemistry strategy.
