Microchannel reactive distillation for the conversion of aqueous ethanol to ethylene

Here we demonstrate the proof-of-concept for microchannel reactive distillation for alcohol-to-jet application:combining ethanol/water separation and ethanol dehydration in one unit operation.Ethanol is first distilled into the vapor phase,converted to ethylene and water,and then the water co-product is condensed to shift the reaction equilibrium.Process intensification is achieved through rapid mass transfer-ethanol stripping from thin wicks using novel microchannel architectures-leading to lower residence time and improved separation efficiency.Energy savings are realized with integration of unit operations.For example,heat of condensing water can offset vaporizing ethanol.Furthermore,the dehydration reaction equilibrium shifts towards completion by immediate removal of the water byproduct upon formation while maintaining aqueous feedstock in the condensed phase.For aqueous ethanol feedstock(40%_w),71% ethanol conversion with 91% selectivity to ethylene was demonstrated at 220℃,600psig,and 0.28 h^(-1) wt hour space velocity.2.7 stages of separation were also demonstrated,under these conditions,using a device length of 8.3 cm.This provides a height equivalent of a theoretical plate(HETP),a measure of separation efficiency,of ^(3).3 cm.By comparison,conventional distillation packing provides an HETP of ^(3)0 cm.Thus,9,1 × reduction in HETP was demonstrated over conventional technology,providing a means for significant energy savings and an example of process intensification.Finally,preliminary process economic analysis indicates that by using microchannel reactive distillation technology,the operating and capital costs for the ethanol separation and dehydration portion of an envisioned alcoholto-jet process could be reduced by at least 35% and 55%,respectively,relative to the incumbent technology,provided future improvements to microchannel reactive distillation design and operability are made.

Study on PVA Membranes Blended with Acrylic Ester-Acrylic Acid Copolymer for Dehydration of Ethanol

The viability of polyvinyl acetate (PVA) membranes blended with acrylic ester-co-acrylic acid copolymers (AE-co-AA), for ethanol dehydration was examined. The effects of the operating temperature on the permeate flux and separation factor of the membranes were investigated. The pervaporation separation characteristics of PVA/(AE-co-AA) membranes were related to the blend ratio, the dose of crosslinking agents and the operating temperature.

Enhancing the separation performance by introducing bioadhesive bonding layer in composite pervaporation membranes for ethanol dehydration

A high performance composite membrane was prepared under the inspiration of bioadhesion principles for pervaporative dehydration of ethanol.Chitosan(CS)and polyacrylonitrile(PAN)ultrafiltration membranes were used as the active layer and the support layer,respectively.Guar gum(GG),a natural bioadhesive,was introduced as the intermediate bonding layer to improve the separation performance and stability of the fabricated CS/GG/PAN composite membranes.The contact angle of the GG layer was just between those of the CS layer and the PAN layer,minimizing the difference of hydrophilicity between the active layer and the support layer.The peeling strength of the composite membrane was significantly enhanced after the introduction of the GG layer.The effects of preparation conditions and operation conditions including GG concentration,operating temperature and ethanol concentration in feed on the pervaporation performance were investigated.The as-fabricated CS/GG/PAN composite membrane showed the optimum performance with a permeation flux of up to804 g·m-2·h-1and a separation factor higher than 1900.Besides,the composite membranes exhibited a desirable long-term operational stability.

Modeling and Optimization of Catalytic Dehydration of Ethanol to Ethylene Using Central Composite Design

The central composite design in the modeling and optimization of catalytic dehydration of ethanol to ethylene was performed to improve the ethylene yield.A total of 20 experiments at random were conducted to investigate the effect of reaction temperature,Si/Al ratios of H-ZSM-5 catalyst and liquid hourly space velocity(LHSV) on the ethylene yield.The results show that the relationship between ethylene yield and the three significant independent variables can be approximated by a nonlinear polynomial model,with R-squared of 99.9%and adjusted R-squared of 99.8%.The maximal response for ethylene yield is 93.4%under the optimal condition of 328 ℃,Si/Al ratio 85,and LHSV 3.8 h-1.

Enhancing Structural Stability and Pervaporation Performance of Composite Membranes by Coating Gelatin onto Hydrophilically Modified Support Layer

The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly （ether sulfone） （PES） support layer was first hydrophilically modified with poly（vinyl alcohol） （PVA） via surface segregation during the phase inversion process. Gelatin （GE） was then cast on the PVA-modified PES support layer as the active layer followed by crosslinking to fabricate composite membranes for ethanol dehydration. The enrichment of PVA on the surface of support layer improved interfacial compatibility of the as-prepared GE/PVA-PES composite membrane. The water contact angle measurement and X-ray photoelectron spectroscopy （XPS） data confirmed the surface segregation of PVA with a surface coverage density of -80%. T-peel test showed that the maxima/force to separate the support layer and the active layer was enhanced by 3 times compared with the GE/PES membrane. The effects of PVA content in the support layer, crosslinking of GE active layer and operating parameters on the pervaporative dehydration performance were investigated. The operational stability of the composite membrane was tested by immersing the membrane in ethanol aqueous solution for a period of time. Stable pervaporation performance for dehydration of 90% ethanol solution was obtained for GE/PVA-PES membrane with a separation factor of -60 and a permeation flux of -1910 g.m^-2.h1 without peeling over 28 days immersion.

Mechanistic Insight into Ethanol Dehydration over SAPO-34 Zeolite by Solid-state NMR Spectroscopy

The reaction mechanism of ethanol dehydration over SAPO-34 zeolite is investigated by using solid-state NMR spectroscopy. SAPO-34 zeolites with different Si contents are prepared and their acidities are characterized by NMR experiments. The higher content of stronger Brønsted acid sites is correlated to the higher Si content. The adsorption of ethanol on the Brønsted acid sites in SAPO-34 leads to the formation of frustrated Lewis pairs(FLPs). Surface ethoxy species is observed by the dehydration of the FLP sites at room temperature, which can be further converted into ethene products. The decomposing of diethyl ether over Brønsted acid sites is responsible for the formation of ethoxy species at higher reaction temperatures. Triethyloxonium ions are formed in the reaction. A plausible reaction mechanism is proposed for the dehydration of ethanol over SAPO-34.

Characterization of Compactness of Rust Layers on Weathering Steels by an Adsorption/Dehydration Test of Ethanol

A new method for evaluating the compactness of rust layers on steels has been proposed in the present study. The method includes adsorption and dehydration process of anhydrous ethanol. The protective ability of rust layers can be qualitatively reflected by the adsorption/dehydration rates. The specific surface area and porosity of rust layers can be calculated by a quantitative model. The results from the present method are consistent with electrochemical tests, N2 adsorption and X-ray diffraction analysis. The method characterizes the compactness of rust layers rather than that of corrosion products removed from the metal surfaces, which is generally practiced in classic N2 adsorption method. Furthermore, the method can reflect the compactness of inner rust layers, to which N2 adsorption is unavailable. The method provides a new approach for the study of rust layers.