Separation of light hydrocarbons with ionic liquids: A review

Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.

Efficient Splitting of Trans-/Cis-Olefins Using an Anion-Pillared Ultramicroporous Metal-Organic Framework with Guest-Adaptive Pore Channels

Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–guest interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.

Efficient capture of C_(2)H_(2)from CO_(2)and C_(n)H_(4)by a novel fluorinated anion pillared MOF with flexible molecular sieving effect

The efficient separation of acetylene(C_(2)H_(2))from carbon dioxide(CO_(2))and CnH_(4)(n=1 and 2)to manufacture high purity C_(2)H_(2)and recover other light hydrocarbons is technologically important,while posing significant challenges.Herein,we reported a new TiF62−anion(TIFSIX)pillared metal-organic framework(MOF)ZNU-5(ZNU=Zhejiang Normal University)with ultramicropores for highly selective C_(2)H_(2)capture with low adsorption heat through gate opening based molecular sieving effect.ZNU-5 takes up a large amount of C_(2)H_(2)(128.6 cm^(3)/g)at 1.0 bar and 298 K but excludes CO_(2),CH_(4),and C_(2)H_(4).Such high capacity has never been realized in MOFs with molecular sieving.The breakthrough experiments further confirmed the highly selective C_(2)H_(2)separation performance from multi-component gas mixtures.3.3,2.8,and 2.2 mmol/g of C_(2)H_(2)is captured at ZNU-5 from equimolar C_(2)H_(2)/CO_(2),C_(2)H_(2)/CO_(2)/CH_(4),and C_(2)H_(2)/CO_(2)/CH_(4)/C_(2)H_(4)mixtures,respectively.Furthermore,2.6,2.0,and 1.5 mmol/g of>98%purity C_(2)H_(2)can be recycled from the desorption process.Combining high working capacity,low adsorption heat,as well as good recyclability,ZNU-5 is promising for C_(2)H_(2)purification.