Simultaneous generation of electricity, ethylene and decomposition of nitrous oxide via protonic ceramic fuel cell membrane reactor

Ethylene,one of the most widely produced building blocks in the petrochemical industry,has received intense attention.Ethylene production,using electrochemical hydrogen pump-facilitated nonoxidative dehydrogenation of ethane(NDE)to ethylene,is an emerging and promising route,promoting the transformation of the ethylene industry from energy-intensive steam cracking process to new electrochemical membrane reactor technology.In this work,the NDE reaction is incorporated into a BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)electrolyte-supported protonic ceramic fuel cell membrane reactor to co-generate electricity and ethylene,utilizing the Nb and Cu doped perovskite oxide Pr_(0.6)Sr_(0.4)Fe_(0.8)Nb_(0.1)Cu_(0.1)O_(3-δ)(PSFNCu)as anode catalytic layer.Due to the doping of Nb and Cu,PSFNCu was endowed with high reduction tolerance and rich oxygen vacancies,showing excellent NDE catalytic performance.The maximum power density of the assembled reactor reaches 200 mW cm^(-2)at 750℃,with high ethane conversion(44.9%)and ethylene selectivity(92.7%).Moreover,the nitrous oxide decomposition was first coupled in the protonic ceramic fuel cell membrane reactor to consume the permeated protons.As a result,the generation of electricity,ethylene and decomposition of nitrous oxide can be simultaneously obtained by a single reactor.Specifically,the maximum power density of the cell reaches 208 mW cm^(-2)at 750℃,with high ethane conversion(45.2%),ethylene selectivity(92.5%),and nitrous oxide conversion(19,0%).This multi-win technology is promising for not only the production of chemicals and energy but also greenhouse gas reduction.

Carbon Capture from Flue Gas Based on the Combination of Non-Contact Hydrophobic Porous Ceramic Membrane and Bubbling Absorption

A hybrid system combined with a non-contact membrane and bubbling absorption is proposed to capture CO_(2) from flue gas.The non-contact way of membrane and liquid absorbent effectively avoids the reduction of gas diffusion flux through the membrane.High-porosity ceramic membranes in hybrid systems are used for gas-solid separation in fuel gas treatment.Due to the high content of H_(2)O and cement dust in the flue gas of the cement plant,the membrane is hydrophobically modified by polytetrafluoroethylene(PTFE)to improve its anti-water,anti-fouling,and self-cleaning performances.The results show that the diffusion flux of CO_(2) through the membrane is still higher than 7.0×10^(−3) mol/m^(2)s(20%CO_(2) concentration)even under the influence of water and cement dust.In addition,slaked lime selected as the absorbent is cheap and the product after bubbling absorption is nano-scale light calcium carbonate.To sum up,the hybrid system combining non-contact membrane and bubbling absorption is expected to be used to capture carbon dioxide from the flue gas of the cement plant.

Corrosion-Resistant Polymer-Derived SiOC Membrane for Effective Organic Removal via Synergistic Adsorption and Peroxymonosulfate Activation

A major challenge is to construct ceramic membranes with tunable structures and functions for water treatment.Herein,a novel corrosion-resistant polymer-derived silicon oxycarbide(SiOC)ceramic membrane with designed architectures was fabricated by a phase separation method and was applied in organic removal via adsorption and oxidation for the first time.The pore structure of the as-prepared SiOC ceramic membranes was well controlled by changing the sintering temperature and polydimethylsiloxane content,leading to a pore size of 0.84–1.62μm and porosity of 25.0–43.8%.Corrosion resistance test results showed that the SiOC membranes sustained minimal damage during 24 h exposure to high-intensity acid–base conditions,which could be attributed to the chemical inertness of SiOC.With rhodamine 6G(R6G)as the model pollutant,the SiOC membrane demonstrated an initial eff ective removal rate of 99%via adsorption;however,the removal rate decreased as the system approached adsorption saturation.When peroxymonosulfate was added into the system,efficient and continuous degradation of R6G was observed throughout the entire period,indicating the potential of the as-prepared SiOC membrane in oxidation-related processes.Thus,this work provides new insights into the construction of novel polymer-derived ceramic membranes with well-defined structures and functions.

Pervaporation Separation of Butanol-Water Mixtures Using Polydimethylsiloxane/Ceramic Composite Membrane

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation performance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40°C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g·m?2·h?1 and 26.1, respectively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.

Design and Fabrication of Ceramic Catalytic Membrane Reactors for Green Chemical Engineering Applications

Catalytic membrane reactors(CMRs),which synergistically carry out separations and reactions,are expected to become a green and sustainable technology in chemical engineering.The use of ceramic membranes in CMRs is being widely considered because it permits reactions and separations to be carried out under harsh conditions in terms of both temperature and the chemical environment.This article presents the two most important types of CMRs:those based on dense mixed-conducting membranes for gas separation,and those based on porous ceramic membranes for heterogeneous catalytic processes.New developments in and innovative uses of both types of CMRs over the last decade are presented,along with an overview of our recent work in this field.Membrane reactor design,fabrication,and applications related to energy and environmental areas are highlighted.First,the configuration of membranes and membrane reactors are introduced for each of type of membrane reactor.Next,taking typical catalytic reactions as model systems,the design and optimization of CMRs are illustrated.Finally,challenges and difficulties in the process of industrializing the two types of CMRs are addressed,and a view of the future is outlined.

Progress on Porous Ceramic Membrane Reactors for Heterogeneous Catalysis over Ultrafine and Nano-sized Catalysts

Heterogeneous catalysts with ultrafine or nano particle size have currently attracted considerable attentions in the chemical and petrochemical production processes, but their large-scale applications remain challenging because of difficulties associated with their efficient separation from the reaction slurry. A porous ceramic membrane reactor has emerged as a promising method to solve the problem concerning catalysts separation in situ from the reaction mixture and make the production process continuous in heterogeneous catalysis. This article presents a review of the present progress on porous ceramic membrane reactors for heterogeneous catalysis, which covers classification of configurations of porous ceramic membrane reactor, major considerations and some important industrial applications. A special emphasis is paid to major considerations in term of application-oriented ceramic membrane design, optimization of ceramic membrane reactor performance and membrane fouling mechanism. Finally, brief concluding remarks on porous ceramic membrane reactors are given and possible future research interests are also outlined.

The Fouling Mechanism of Ceramic Membranes Used for Recovering TS-1 Catalysts

Ceramic ultrafiltration membranes were used to separate titanium silicalite-1 （TS-1） catalysts from the slurry of catalytic ammoximation of cyclohexanone to oxime. Silica was shown to have a great effect on membrane fouling in the alkaline environment of this system. In the ammoximation system, there are three main silica sources, which are residual silica on the catalyst particles surface during preparation, silica dissolved from TS-1 catalyst particles by ammonia solvent, and silica sol added into the reaction slurry to inhibit the dissolution erosion of the TS-1 catalyst. The silica dissolved by ammonia has been proved to influence membrane fouling most among the three silica sources. This was because the amount of silica dissolved by ammonia was the largest, and the polymerization of silica monomers at high concentration caused colloid particles formation, which led to a dense cake layer depositing on the membrane surface. Meanwhile, the size reduction of catalyst particles caused by alkaline dissolution also increased specific resistances of cake layers.

Preparation of Monodispersed O/W Emulsion by Ceramic External Membrane Emulsification System——Preliminary Study on Integrated Ceramic Membrane Emulsification Reactor

A new reactor with integrated conventional slurry stirred reactor and ceramic external membrane emulsification system, was introduced in this paper. Toluene and toluene containing surfactant was separately used as dispersed phase for preparation of emulsions. Two kinds of emulsions were prepared and compared. The volume average sizes of prepared emulsions were 3.53μm and 3.6μm respectively. The results showed that the droplet sizes of two kinds of emulsions were similar, but the monodispersed emulsion was only obtained with addition of surfactant into the dispersed phase.

Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation

Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.

One-step Continuous Phenol Synthesis Technology via Selective Hydroxylation of Benzene over Ultrafine TS-1 in a Submerged Ceramic Membrane Reactor

A new route towards phenol production by one-step selective hydroxylation of benzene with hydrogen peroxide over ultrafine titanium silicalites-1(TS-1) in a submerged ceramic membrane reactor was developed, which can maintain the in situ removal of ultrafine catalyst particles from the reaction slurry and keep the process continuous.The effects of key operating parameters on the benzene conversion and phenol selectivity, as well as the membrane filtration resistance were examined by single factor experiments. A continuous reaction process was carried out under the obtained optimum operation conditions. Results showed that the system can be continuously and stably operated over 20 h, and the benzene conversion and phenol selectivity kept at about 4% and 91%, respectively. The ceramic membrane exhibits excellent thermal and chemical stability in the continuous reaction process.

Feasibility analysis of SO_2 absorption using a hydrophilic ceramic membrane contactor

Hydrophilic ceramic membranes would be potential candidates for membrane gas absorption if they could be applied to appropriate separation processes.This study highlights a novel concept for the practical implementation of SO_2 absorption in hydrophilic ceramic membrane that exhibits outstanding thermal and mechanical stabilities.With this aim,we investigated experimentally the performance of SO_2 absorption into aqueous sodium hydroxide (NaOH) solution in a hydrophilic alumina (Al_2O_3) membrane contactor in terms of SO_2 removal efficiency and SO_2 mass transfer flux,and compared the performance with that in a hydrophobic one.A series of experiments were performed at various conditions over a NaOH concentration range of 0–1.0 mol·L^(-1),a liquid flow rate range of 30–180 ml·min^(-1),a gas flow rate range of 120–1000 ml·min^(-1),an inlet SO_2 concentration range of 400–2000μl·L^(-1),and a temperature range of 10–35°C.It was found that the hydrophilic membrane was more competitive when using a NaOH concentration higher than 0.2 mol·L^(-1).Furthermore,it can be inferred that the hydrophilicα-Al_2O_3 membrane exhibited exceptional long-term stability under 480 h continuous operation.

Modeling of the Relationship Between Pore Size Distribution and Thickness of Ceramic MF Membrane

The pore size distribution(PSD)measured by the gas bubble point(GBP)method ofceramic microfiltration(MF)membranes prepared by suspension technique was found to be signifi-cantly influenced by the membrane thickness.A culm-like model for pore structure was introduced tocharacterize the membrane pores instead of the conventional model which does not reflect the radiusvariation along the pore passages and is unable to explain the thickness effect on the membrane PSD.A laminate structure,taking the culm-like model for pore structure into consideration,was hypoth-esized for ceramic MF membranes.A mathematical model was then established to quantitativelydescribe the relationship between the membrane number PSD and the membrane thickness.Goodresults were obtained for the correlation of mean pore size and simulation of the PSD for ceramicMF membranes.

Polymer/Ceramic Composite Membranes and Their Application in Pervaporation Process

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.

Hydrogen Permeation Properties of Perovskite-type BaCe_(0.9)Mn_(0.1)O_(3-δ)Dense Ceramic Membrane

The electrical conduction properties of dense BaCe0.9Mn0.1O3-d (BCM10) membrane were investigated in the temperature range of 600-900oC. High ionic and electronic conductivities at elevated temperatures make BCM10 a potential ceramic material for hydrogen separation. Hydrogen permeation through BCM10 membranes was studied using a high- temperature permeation cell. Little hydrogen could be detected at the sweep side. However, appreciable hydrogen can permeate through BCM10 membrane coated with porous platinum black, which shows that the process of hydrogen permeation through BCM10 membranes was controlled by the catalytic decomposition and recomposition of hydrogen on the surfaces of BCM10 membranes.

Effect of Cross-flow Velocity on the Critical Flux of Ceramic Membrane Filtration as a Pre-treatment for Seawater Desalination

Pre-treatment, which supplies a stable, high-quality feed for reverse osmosis （RO） membranes, is a criti- cal step for successful operation in a seawater reverse osmosis plant. In this study, ceramic membrane systems were employed as pre-treatment for seawater desalination. A laboratory experiment was performed to investigate the effect of the cross-flow velocity on the critical flux and consequently to optimize the permeate flux. Then a pilot test was performed to investigate the long-term performance. The result shows that there is no significant effect of the cross-flow velocity on the critical flux when the cross-flow velocity varies in laminar flow region only or in turbulent flow region only, but the effect is distinct when the cross-flow velocity varies in the transition region. The membrane fouling is slight at the permeate flux of 150 L·m^-2·h^-1 and the system is stable, producing a high-quality feed （the turbidity and silt density index are less than 0.1 NTU and 3.0, respectively） for RO to run for 2922.4 h without chemical cleaning. Thus the ceramic membranes are suitable to filtrate seawater as the pre-treatment for RO.

Preparation of Macroporous TiO2 Ceramic Based on Membrane Jet-flow Emulsification

A novel method to prepare macroporous TiO2 ceramic, based on membrane emulsification was reported.To solve the paradox between the instability of nonaqueous emulsion and long emulsification time required by themembrane emulsification, a two-stage ceramic membrane jet-flow emulsification .was. proposed. Discussion wasconducted on the evolution of droplet size with time, which followed the Ostwalcl npemng theory. And a monodispersed nonaqueous emulsion with an average droplet size of 1.6μm could beprepared. Using the emulsion, as atemplate, TiO2 ceramics with an average pore size ot 1.1 μm were obtaineed. Tne material could be prospectivelyused for preparation of catalysts, adsorbents, and membranes.

Superhydrophobic modification of ceramic membranes for vacuum membrane distillation

The hydrophobically modi fied ceramic membranes have great potential for energy-ef ficient membrane distillation.In this work,flat-sheet ceramic membranes with a superhydrophobic surface were fabricated by grafting 1H,1H,2H,2H-per fluorooctyltrichlorosilane or 1H,1H,2H,2H-per fluorodecyltriethoxysilane and followed by ultraviolet irradiation.The surface water contact angle was improved from 46° of original ceramic membrane to 159°,which exhibited a stable and excellent superhydrophobic effect.The modi fied membranes showed a high flux of 27.28 kg·m^(-2)·h^(-1) and simultaneously maintained an excellent retention rate of 99.99%,when used in vacuum membrane distillation process for treatment of a 1 wt% NaCl(75 °C) aqueous solution.These results suggested that superhydrophobic modi fication of ceramic surface is a facile and cost-effective way to achieve higher membrane distillation performance.The superhydrophobically-modi fied ceramic membrane with an excellent desalination capacity would show considerable potential in practical membrane distillation utilizations.

CFD simulation of flow field and resistance in a 19-core tandem ceramic membrane module

CFD simulation of the permeation process of a 19-core tandem ceramic membrane module was established to investigate flow field and resistance and its change in permeate flux to the membrane element position and the channel of each membrane element.The results show that when the volume flow rate changes from26 m3·h-1 to 89 m3·h-1,the resistance of each part of the membrane module increases gradually.The increase in resistance loss in the membrane element is faster than the plates and the bell mouths.In a single ceramic membrane module,the maximum difference in flow rate of each membrane tube is 7.23%.In a single membrane tube,the outer ring channels 3–5,3–6,3–7,3–8 are relatively slow.The maximum mass flow deviation from the mean is 2.7%.This work helps to clarify the flow mechanism within the modules,optimize the structure of the equipment and provide a reliable basis for the improvement of industrial ceramic membrane modules.

Polydimethylsiloxane (PDMS) Composite Membrane Fabricated on the Inner Surface of a Ceramic Hollow Fiber: From Single-Channel to Multi-Channel

The fabrication of a separation layer on the inner surface of a hollow fiber (HF) substrate to form an HF composite membrane offers exciting opportunities for industrial applications, although challenges remain. This work reports on the fabrication of a polydimethylsiloxane (PDMS) composite membrane on the inner surface of a single-channel or multi-channel ceramic HF via a proposed coating/crossflow approach. The nanostructures and transport properties of the PDMS HF composite membranes were optimized by controlling the polymer concentration and coating time. The morphology, surface chemistry, interfacial adhesion, and separation performance of the membranes were characterized by fieldemission scanning electron microscope (FE-SEM), attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy, the nano-indentation/scratch technique, and pervaporation (PV) recovery of bio-butanol, respectively. The formation mechanism for the deposition of the PDMS layer onto the inner surface of the ceramic HF was studied in detail. The optimized inner surface of the PDMS/ceramic HF composite membranes with a thin and defect-free separation layer exhibited a high flux of ~1800 gm-2h-1 and an excellent separation factor of 35–38 for 1 wt% n-butanol/water mixtures at 60
C. The facile coating/cross-flow methodology proposed here shows great potential for fabricating inner-surface polymer-coated HFs that have broad applications including membranes, adsorbents, composite materials, and more.

Easy Fabrication of Dense Ceramic Membrane for Oxygen Separation

A combined EDTA-citrate complexing method was developed for the easy preparation of mixed oxygen-ionic and electronic conducting dense ceramic membrane for oxygen separation. The nea method takes the advantage of lower calcination temperature for phase formation. lower membrane sintering temperature and higher relative density over the standard ceramic method.