Dual-Role Membrane as NH3 Permselective Reactor and Azeotrope Separator in Urea Alcoholysis.
ABSTRACT: Urea methanolysis is a green alternative to synthesize dimethyl carbonate (UM-to-DMC). However, it is strongly challenged by the generated NH3 induced thermodynamic equilibrium limitation and the azeotropic products' separation. Herein, these predicaments are well-relieved by introducing membranes in both reaction and product separation. An NH3 permselective membrane reactor (MR) based on modified SAPO-34 membrane is successfully realized for UM-to-DMC. The permselectivity and acidity of the SAPO-34 membrane are significantly adjusted to cater the strict molecular sieving of NH3/methanol and chemical inertness upon the reaction. The MR exhibits excellent reactant conversion and DMC selectivity, resulting in >139% higher DMC yield than that of the nonmembrane reactor, due to in situ removal of NH3 by the membrane. The MR also demonstrates reliable chemical, thermal, and mechanical stability during >2000 h. Moreover, the regular SAPO-34 membrane with controlled thickness presents remarkable separation performance for the methanol-DMC azeotrope, in which the methanol-DMC separation factors and the methanol permeance are 1-2 orders of magnitude higher than those of the polymeric membranes. This study suggests the great potential that integration of such membranes offers for process intensification, energy savings, and efficiency improvement in a series of urea alcoholysis and even other NH3 releasing reactions.
Project description:The reaction of methanol to light olefins and water (MTO) was studied in a fixed bed tubular membrane reactor using commercial SAPO-34 catalyst. In the fixed bed reactor without membrane support, the MTO reaction collapsed after 3?h time on stream. However, if the reaction by-product steam is in?situ extracted from the reactor through a hydrophilic tubular LTA membrane, the reactor produces long-term stable about 60?% ethene and 10?% propene. It is shown that the reason for the superior performance of the membrane-assisted reactor is not the prevention of catalyst damage caused by steam but the influence of the water removal on the formation of different carbonaceous residues inside the SAPO-34 cages. Catalytically beneficial methylated 1 or 2 ring aromatics have been found in a higher percentage in the MTO reaction with a water removal membrane compared to the MTO reaction without membrane support.
Project description:A new class of TiO2-doped CeO2 nanorods was synthesized via a modified hydrothermal method, and these nanorods were first used as catalysts for the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH in a fixed-bed reactor. The micromorphologies and physical-chemical properties of nanorods were characterized by transmission electron microscopy, X-ray diffraction, N2 adsorption, inductively coupled plasma atomic emission spectrometry, X-ray photoelectron spectroscopy, and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The effects of the TiO2 doping ratio on the catalytic performances were fully investigated. By doping TiO2, the surface acid-base sites of CeO2 nanorods can be obviously promoted and the catalytic activity can be raised evidently. Ti0.04Ce0.96O2 nanorod catalysts exhibited remarkably high activity with a methanol conversion of 5.38% with DMC selectivity of 83.1%. Furthermore, kinetic and mechanistic investigations based on the initial rate method were conducted. Over the Ti0.04Ce0.96O2 nanorod catalyst, the apparent activation energy of the reaction was 46.3 kJ/mol. The reaction rate law was determined to be of positive first-order to the CO2 concentration and the catalyst loading amount. These results were practically identical with the prediction of the Langmuir-Hinshelwood mechanism in which the steps of CO2 adsorption and activation are considered as rate-determining steps.
Project description:Cu/SAPO-34 catalysts are prepared using solid-state ion exchange (SSIE) and liquid ion exchange (LIE). SSIE is conducted by calcining a physical mixture of H-SAPO-34 zeolite and CuO nanoparticles at elevated temperatures (500-800 °C). The conventional LIE method is conducted by exchanging Na-SAPO-34 with Cu(COOCH3)2 aqueous solution with a final calcination step at 500 °C. Catalysts were fully characterized, focusing on Cu species identification. The NH3-SCR activity is evaluated for NO x removal. Cu/SAPO-34 catalysts synthesized by SSIE at 700 °C achieved an optimal reaction rate, which was correlated with a higher proportion of Cu2+ ions. The activation energies of Cu/SAPO-34 catalysts prepared by SSIE and LIE with varying copper loadings are 32-38 and 42-47 kJ mol-1, respectively. The SSIE catalysts achieve higher turnover frequency than LIE catalysts for a similar copper content, which decreases on increasing the copper loading. These results provide evidence that Cu ions exchanged into the Cu/SAPO-34 catalysts synthesized by SSIE present higher activity than those prepared by LIE for NO x removal by NH3-SCR.
Project description:This work reports the preparation, characterization, and O2/N2 separation properties of composite membranes based on the polymer of intrinsic microporosity (PIM-1) and the zeolitic imidazolate framework (ZIF-8). Especially, the composite membranes were prepared by growing ZIF-8 nanoparticles on one side of the PIM-1 membrane in methanol. Fourier transform infrared spectroscopy and thermo-gravimetric analysis indicated that there is no strong chemical interaction between ZIF-8 nanoparticles and PIM-1 chains. Scanning electron microscopy images showed that ZIF-8 nanoparticles adhere well to the PIM-1 membrane surface. The pure-gas permeation results confirmed that growth of ZIF-8 on the PIM-1 membrane can enhance the performance of O2/N2 separation. Particularly, the O2/N2 separation performance of the PIM-1/ZIF-8-7 composite membrane exceeds the Robeson upper bound line.
Project description:Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005-0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu-CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol(-1) and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce(4+) sites to Ce(3+) based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce(3+) content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu-CeO2 catalyst (0.5 wt% of Cu). Moreover, the content of reduced Ce(3+) sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu-CeO2 catalyst (0.1 wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy.
Project description:The biomass concentrator reactor (BCR), a gravity flow membrane bioreactor (MBR) design, was evaluated for use in treating a municipal wastewater stream. The BCR operates with less than 2.5 cm of pressure head and uses a 3 to 4 mm thick tortuous path membrane with pore size ranging from 18 to 28 ?m to achieve solids separation. A two-stage, aerobic/anoxic reactor was evaluated for the removal of chemical oxygen demand (COD), ammonia, total nitrogen, and solids separation. The reactor was fed 72 L/day, with a hydraulic retention time of 9.3 hours, and had a solids retention time of 20 days. The influent COD was reduced by 93%, whereas, influent ammonia was reduced below 0.1 mg/L and total nitrogen was reduced by 53.7%. A lack of readily biodegradable COD limited denitrification and thus total nitrogen removal. The reactor solids were retained completely in the reactor by the membrane for the duration of testing.
Project description:Novel visible-light responded aluminosilicophosphate-5 (SAPO-5)/g-C3N4 composite has been easily constructed by thermal polymerization for the mixture of SAPO-5, NH4Cl, and dicyandiamide. The photocatalytic activity of SAPO-5/g-C3N4 is evaluated by degrading RhB (30 mg/L) under visible light illumination (? > 420 nm). The effects of SAPO-5 incorporation proportion and initial RhB concentration on the photocatalytic performance have been discussed in detail. The optimized SAPO-5/g-C3N4 composite shows promising degradation efficiency which is 40.6% higher than that of pure g-C3N4. The degradation rate improves from 0.007 min-1 to 0.022 min-1, which is a comparable photocatalytic performance compared with other g-C3N4-based heterojunctions for dye degradation. The migration of photo-induced electrons from g-C3N4 to the Al site of SAPO-5 should promote the photo-induced electron-hole pairs separation rate of g-C3N4 efficiently. Furthermore, the redox reactions for RhB degradation occur on the photo-induced holes in the g-C3N4 and Al sites in SAPO-5, respectively. This achievement not only improves the photocatalytic activity of g-C3N4 efficiently, but also broadens the application of SAPOs in the photocatalytic field.
Project description:A titanium-based zeolitic thiophene-benzimidazolate framework has been designed for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide. The developed catalyst activates carbon dioxide and delivers over 16% yield of DMC without the use of any dehydrating agent or requirement for azeotropic distillation.
Project description:Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium (Pd) nanoparticles. The modified membranes were evaluated for antibacterial and antifouling efficacy in a monoculture species biofilm (i.e., drip flow biofilm reactor, DFR) and mixed species biofilm experiment (i.e., aerobic membrane reactor, AeMBR). 1,2,3-triazole and Pd nanoparticles inhibited growth of Pseudomonas aeruginosa in both aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide within the monoculture species biofilm matrix. When the modified membranes were connected to AeMBR, the increase in transmembrane pressure was lower than that of the non-modified membranes. This was accompanied by a decrease in protein and polysaccharide concentrations within the mixed species biofilm matrix. Biomass amount in the biofilm layer was also lower in the presence of modified membranes, and there was no detrimental effect on the performance of the reactor as evaluated from the nutrient removal rates. 16S rRNA analysis further attributed the delay in membrane fouling to the decrease in relative abundance of selected bacterial groups. These observations collectively point to a lower fouling occurrence achieved by the modified membranes.
Project description:Almost all covalent organic framework (COF) materials conventionally fabricated by solvothermal method at high temperatures and pressures are insoluble and unprocessable powders, which severely hinder their widespread applications. This work develops an effective and facile strategy to construct flexible and free-standing pure COF membranes via the liquid-liquid interface-con?ned reaction at room temperature and atmospheric pressure. The aperture size and channel chemistry of COF membranes can be rationally designed by bridging various molecular building blocks via strong covalent bonds. Benefiting from the highly-ordered honeycomb lattice, high solvent permeances are successfully obtained and follow the trend of acetonitrile > acetone > methanol > ethanol > isopropanol. Interestingly, the imine-linked COF membrane shows higher nonpolar solvent permeances than b-ketoenamine-linked COF due to their difference in pore polarity. Both kinds of COF membranes exhibit high solvent permeances, precise molecular sieving, excellent shape selectivity, and sufficient flexibility for membrane-based separation science and technology.