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Gas-liquid membrane contactor (GLMC) has been regarded as a promising alternative to conventional contacting processes for CO 2 absorption. In this work, a composite hollow fiber (HF) membrane with an aminosilane-modified zeolitic imidazolate framework-8 (mZIF-8) based dense skin layer was designed and synthesized for high-efficiency biogas upgrading in the GLMC process, by dispersing mZIF-8 nanocrystals into poly(dimethylsiloxane) matrix and then depositing on a porous polyvinylidene fluoride (PVDF) substrate. (3-aminopropyl)triethoxysilane was introduced to modify the ZIF-8 nanocrystals, thereby enabling the chemical bonding with PDMS chains for avoiding interfacial voids and further enhancing hydrophobicity. Compared with the control membrane, the newly developed mZIF-8 based composite membrane with a dense skin exhibited competitive hydrophobicity with a contact angle of 130°, ensuring its anti-wetting ability. It exhibited an enhanced biogas upgrading performance with the absorption fluxes of 2.3 and 3.8 × 10−3 mol m−2·s−1 using water and 1 M monoethanolamine (MEA) as absorbents, respectively (liquid velocity = 0.25 m s−1). In particular, a comparable selectivity of CO 2 /CH 4 with the value of ∼20 was achieved by using MEA as absorbent in the GLMC process. A robust long-term stability of the mZIF-8 based composite HF membrane was also achieved in a 15-day operation. This work offers a new perspective for promoting CO 2 mass transfer with mZIF-8 based composite HF membranes, thereby improving the biogas upgrading performance in GLMC applications. • A composite hollow fiber membrane with a ZIF-8 based dense skin layer was designed and synthesized. • The ZIF-8 nanocrystals were modified to cross-link with PDMS chains for further hydrophobicity enhancement. • The newly developed membrane exhibited competitive hydrophobicity, ensuring its anti-wetting ability. • An enhanced biogas upgrading performance was achieved in gas-liquid membrane contact applications. [ABSTRACT FROM AUTHOR]

An inorganic-organic fluorinated titania-silica (fTiO 2 -SiO 2 )/polyvinylidene fluoride (PVDF) composite membrane was fabricated, via facile in-situ vapor-induced hydrolyzation method followed by hydrophobic modification. This low mass-transfer-resistance membrane, composing of a mesoporous layer deposited onto macroporous substrate, was designed for biogas upgrading in gas-liquid membrane contactor (GLMC) application. The surface hydroxylation was introduced to facilitate the bridging of TiO 2 -SiO 2 nanoparticles and PVDF substrate, which resulted in a more coherent deposition of the fTiO 2 -SiO 2 layer onto the substrate. The surface microstructure was fine-tuned by controlling the amount of doped Si precursor, forming an integrated mesoporous fTiO 2 -SiO 2 layer. The resultant fTiO 2 -SiO 2 /PVDF composite hollow fiber membrane exhibited a tighter pore size of ~25 nm and a desired water contact angle of ~124°, which effectively prevented membrane wetting. The CO 2 absorption fluxes of 8.0 and 5.6 × 10 −3 mol m −2 s −1 were achieved due to the lower mass transfer resistance, by using 1 M of monoethanolamine (MEA) and sodium taurinate as absorbents with a liquid velocity of 0.25 m s −1 , respectively. The long-term stability test showed a good integrity between the fTiO 2 -SiO 2 layer and the PVDF substrate after 31-days of GLMC operation. The main benefit is the robust fluorinated inorganic layer which exhibited strong chemical resistance and high hydrophobicity, thus preventing membrane damage and pore wetting. Overall, this work provides an insight into the preparation of high–performance inorganic/organic composite hollow fiber membranes for carbon dioxide (CO 2 ) removal in GLMC application. [ABSTRACT FROM AUTHOR]