Separation and Purification of Furans from n-Butanol by Zeolitic Imidazole Frameworks: Multicomponent Adsorption Behavior and Simulated Moving Bed Process Design

Abstract

Biomass-derived furanic chemicals such as 2,5dimethylfuran (DMF) are significant biorefining targets with potential as biofuels and aromatic feedstocks, and processes for their large-scale production are hence of interest. The development of efficient and low-cost processes for DMF purification from dilute multicomponent reactor exit streams is a key challenge. Here we develop an adsorption-based separation process that utilizes zeolitic imidazolate framework-8 (ZIF-8) as the active material, which directly upgrades dilute (<10 wt %) furanic streams to a high-purity product. We combine multicomponent adsorption measurements with the detailed design of a simulated moving-bed (SMB) process for high-purity furanics (primarily DMF) production and concurrent generation of a purified solvent (n-butanol, BuOH) recycle stream. Upon the basis of the hypothesis that hydropobic ZIF materials may allow enhanced furanic adsorption selectivity over alcohols, we investigate several ZIFs via unary adsorption measurements and ideal adsorbed solution theory (IAST) predictions. ZIF-8 is found to have particularly favorable furan-selective behavior. We then develop an initial version of a simulated moving bed (SMB) separation process with a realistic multicomponent feed stream which also includes methylfuran (MF) byproduct and the ethyl acetate (EtAc) desorbent. Iterative refinement of the multicomponent adsorption model as well as detailed dynamic SMB simulations together allow convergence to a process that satisfies extract and raffinate purity and recovery requirements. The ZIF-based SMB process is predicted to reach a productivity > 100 kg DMF/(m 3 adsorbent•h), which is similar to those of current SMB processes for production of petrochemical aromatics such as p-xylene.

Metal−Organic Frameworks for Liquid Phase Applications

“…The ZIF‐based SMB was predicted to reach a productivity similar to those of current SMB processes for the production of petrochemical aromatics such as p ‐xylene. [ 65 ]…”

“…The ZIF-based SMB was predicted to reach a productivity similar to those of current SMB processes for the production of petrochemical aromatics such as p-xylene. [65] Meanwhile, MOF-based membranes have been investigated for biofuel purification. By dispersing [Cu 2 (bza) 4 (pyz)] (bza = benzoate, pyz = pyrazine) into PDMS to form a MMM, Takamizawa et al attempted to separate alcohol/water mixtures by pervaporation.…”

Purification of rutin by supercritical fluid simulated moving bed chromatography

“…[20] In the early 1960s, the UOP Company first applied SMB technology to the separation of xylene in the petrochemical production process, and currently SMB is widely used in the sugar industry [21] and in separation of natural products and fine chemicals. [22] Azenha et al [23] obtained raffinate stream with a purity of 99.0% for betulinic and oleanolic acid in the extract stream with 99.4% purity. Li et al [24] investigated the feasibility of xylo-oligosaccharides purification by sequential simulated moving bed (SSMB).…”

Separation and Purification of 2,5-Dimethylfuran: Process Design and Comparative Technoeconomic and Sustainability Evaluation of Simulated Moving Bed Adsorption and Conventional Distillation

“…More recently, we demonstrated the remarkable furanic adsorption selectivity of ZIF-8 from a multicomponent mixture of furanics, BuOH, and ethyl acetate (EtAc). 25 The latter was chosen as the desorbent due to its effectiveness in displacing DMF from ZIF-8, its high volatility (useful for easier separation), and its high sustainability index (since it can be easily made from biomass-derived acetic acid and ethanol). We obtained detailed multicomponent adsorption data and used them to parameterize initial adsorption models.…”

“…For simulations of the adsorptive process, more accurate multicomponent adsorption models were developed and used, based upon the experimental data in our previous work. 25 After applying heat integration and other process intensification techniques, a technoeconomic analysis was performed to differentiate these processes. We discuss the sensitivity of our results to key process variables and discuss the potential direct economic and environmental impacts of our findings.…”