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.

Preparation of Al_2O_3-SiO_2-TiO_2-ZrO_2 Composite Ceramic Membranes by Sol-Gel Method

Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.

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.

Preparation of defect free ceramic/Ti composite membranes by surface modification and in situ oxidation

Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.

Nanocomposite Membranes based on Perfl uorosulfonic Acid/Ceramic for Proton Exchange Membrane Fuel Cells

Perfl uorosulfonic acid/ceramic nanocomposite membranes were investigated as electrolytes for polymer electrolyte membrane fuel cell applications under low relative humidity. Different nanosized ceramics（SiO2, ZrO2, TiO2） with diameters in the range of 2-6 nm were synthesized in situ in Nafion solution through a sol-gel process and the formed nanosized ceramics were well-dispersed in the solution.The nanocomposite membranes were formed through a casting process. The nanocomposite membrane showes enhanced water retention ability and improved proton conductivity compared to those of pure Nafi on membrane. The mechanical strength of the formed nanocomposite membranes is slightly less than that of pure Nafi on membrane. The experimental results demonstrate that the polymer ceramic nanocompsite membranes are potential electrolyte for fuel cells operating at elevated temperature.

Multilayer Membranes Based on Ceramic Materials——Sol-gel Synthesis,Characterization and Membrane Performance

In nearly all chemical and petrochemical systems, separation of products generally accounts for more than 50% of the capital cost and the greatest part of the energy consumption. It is generally believed that membrane systems can offer benefits in both reducing the energy consumption of the separation stages and lowering the capital expenditure （CAPEX）. Microporous ceramic membranes have the potential to overcome the limitation in polymer membranes operation, which has been the subject of a large amount of research worldwide in the last two decades. And most of the research has aimed at the production of the asymmetric multilayered membrane based on amorphous oxides by sol-gel techniques. The paper is to give an overview of publications on ceramic membranes, including less common materials of titania, zirconia, which can be used for pervaporation in corrosive media. Commercially available microporous membranes based on these membrane materials and the membrane economics are also summarized.

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.

Synthesis and Microstructure of Doped Alumina Composite Membrane by Sol-Gel Process

The supported membranes of Al 2O 3 and its modification membranes were prepared.Al 2O 3,Al 2O 3 SiO 2 TiO 2 and Al 2O 3 SiO 2 TiO 2 ZrO 2 membranes were mamufatured by the slip casting process using mixing boehmite,silicate,titania and zirconia sols under proper conditions,then the composite membrane was prepared.The structure and characteristics of the membrane were determined by XRD,SEM and AFM measurement.The conditions of preparation of the membrane are discussed.The thickness of the layer is about 1-2μm,the diameter of an average pore is 200-300nm and has a narrow pore distribution without crack forming.By changing the ratios of Al∶Si∶Ti∶Zr(mol),variations of surface pore size of Al 2O 3 SiO 2 TiO 2 ZrO 2 membrane can be gained.

PREPARATION AND SEPARATING PROPERTIES OF MoS_2/γ-Al_2O_3 CERAMIC COMPOSITE MEMBRANE FOR H_2S-H_2 MIXTURE

MoS2/γ－Al2O3 ceramic composite membrane is successfully synthesized by the sol-gel method based on the inorganic salt route. The aluminum hydrate sol derived from the inorganic salt Al(NO3)3, whose transparence and viscosity are 97% and 1.2 × 10-3 Pa. s, respectively, can be formed through adjusting the ratio of the peptizing agent H+ to Al3+ to 0.3. The aluminum hydrate gel at 110℃ is amorphous in structure and is heat-treated in air at 800℃ to form γ－Al2O3. The precursor derived from the mixture solution of ammonium molybdate, thioacetamide and a reducing agent, can be transformed into crystal MoS2 under reducing condition at 800℃. MoS2/γ－Al2O3 composite membrane is an organic whole and bps no gradation from MoS2 layer to γ－Al2O3 Iayer. The separation factor a H2/H2S through the MoS2/γ－Al2O3 composite membrane increase with rising temperature and a H2/H2S at 600℃ is 4.45 higher than the theoretical separation factor produced by the ideal Knudsen diffusion.

Effects of Sn residue on the high temperature stability of the H_2-permeable palladium membranes prepared by electroless plating on Al_2O_3 substrate after SnCl_2–PdCl_2 process: A case study

The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.

Development of CO2 Selective Poly（Ethylene Oxide）-Based Membranes： From Laboratory to Pilot Plant Scale

Membrane gas separation is one of the most promising technologies for the separation of carbon dioxide （CO2） from various gas streams. One application of this technology is the treatment of flue gases from combustion processes for the purpose of carbon capture and storage. For this application, poly（ethylene oxide）-containing block copolymers such as Pebax or PolyActiveTM polymer are well suited. The thin-film composite membrane that is considered in this overview employs PolyActiveTM polymer as a selective layer material. The membrane shows excellent CO2 permeances of up to 4 m^3（STP）.（m^2·h·bar）^-1 （1 bar = 105 Pa） at a carbon dioxide/nitrogen （CO2/N2） selectivity exceeding 55 at ambient temperature. The membrane can be manufactured reproducibly on a pilot scale and mounted into fiat-sheet membrane modules of different designs. The operating performance of these modules can be accurately predicted by specifically developed simulation tools, which employ single-gas permeation data as the only experimental input. The performance of membranes and modules was investigated in different pilot plant studies, in which flue gas and biogas were used as the feed gas streams. The investigated processes showed a stable separation performance, indicating the applicability of PolyActiveTM polymer as a membrane material for industrialscale gas processing.

Oily Water Treatment by Ceramic Membrane: Modeling and Simulation

The separation process of oily water using membranes has attracted the attention of researchers and engineers. The greater problem in the use of membrane separation process is the reduction in permeate flux due to clogged pores by oil deposition inside the membrane or by the effect of the concentration polarization. For this purpose, a theoretical study of a water/oil separation module was performed. This device consists of a tubular ceramic membrane provided with a rectangular inlet section. Numerical simulations were performed using Ansys CFX software to solve the mass and momentum conservation equations in the fluid and porous domains. Here was adopted the RNG k-ε turbulence model. The effect of the membrane porosity and the inlet velocity of the fluid mixture on the two-phase flow behavior inside the separation module were evaluated. Results of the volumetric fraction, velocity and pressure fields of the oil and water phases are presented and analyzed. The results indicate a higher oil concentration within the membrane for the cases of higher porosity, and that the inlet fluid mixture velocity does not substantially affect the velocity profile within the separation module. It is found that the maximum separation efficiency of the module was obtained with feed velocity of 40 m/s and membrane porosity of 0.44.

Palladium/ceramic composite membranes prepared by novel electroless plating procedure

THIN films have become more and more important in advanced technology,hence attracted theresearch interest in material science and technology.In chemistry,thin films are classified intoorganic and inorganic membranes.Compared with organic membranes,inorganic membranesexhibit high-temperature stability and surface modifications,and have potential

Acid precipitation coupled membrane-dispersion advanced oxidation process(MAOP)to treat crystallization mother liquor of pulp wastewater

Treatment to crystallization mother liquor containing high concentration of organic and inorganic substances is a challenge in zero liquid discharge of industrial wastewater.Acid precipitation coupled membrane-dispersion advanced oxidation process(MAOP)was proposed for organics degradation before salt crystallization by evaporation.With acid-MAOP treatment CODCrin mother liquor of pulping wastewater was eliminated by 55.2%from ultrahigh initial concentration up to 12,500 mg·L^-1.The decolorization rate was 96.5%.Recovered salt was mainly NaCl(83.3 wt%)having whiteness 50 brighter than industrial baysalt of whiteness 45.The oxidation conditions were optimized as CO3=0.11 g·L^-1 and CH2O2=2.0 g·L^-1 with dispersing rate 0.53 ml·min^-1 for 100 min reaction toward acidified liquor of p H=2.Acidification has notably improved evaporation efficiency during crystallization.Addition of H2O2 made through membrane dispersion has eliminated hydroxyl radical"quench effect"and enhanced the degradation capacity,in particular,the breakage of carbon-chloride bonds(of both aliphatic and aromatic).As a result,the proposed coupling method has improved organic pollutant reduction so as the purity of salt from the wastewater mixture which can facilitate water and salt recycling in industry.

PREPARATION OF SILICA MOLECULAR SIEVE MEMBRANE FOR HYDROGEN SEPARATION

A ceramic tube supported γ alumina silica inorganic composite membrane was made by modifying a ceramic tube supported γ alumina film with a silica sol using sol gel method. The thickness of the silica thin film was 750? and the pore diameter was less than 5?.The prepared silica molecular sieve membrane displayed a high hydrogen permeability and high selectivities of H 2/N 2 and H 2/CO 2 gas mixtures. This composite membrane can be used to separate high purity hydrogen of more than 99 5% from various kinds of industrial waste gas mixtures containing hydrogen.

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon （BAC） （Process A） and ceramic membrane-BAC （Process B） were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm （UV254, a parameter indicating organic matter with aromatic structure） were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.

Hydroxyl radical intensified Cu2O NPs/H2O2 process in ceramic membrane reactor for degradation on DMAc wastewater from polymeric membrane manufacturer

High-concentration industrial wastewater containing N,N-dimethylacetamide(DMAc)from polymeric membrane manufacturer was degraded in Cu2O NPs/H2O2 Fenton.process.In the membrane assisted Fenton process DMAc removal rate was up to 98%with 120 min which was increased by 23%over the batch reactor.It was found that:OH quench time was extended by 20 min and the maximum:0H productivity was notably 88.7%higher at 40 min.The degradation reaction rate constant was enhanced by 2.2 times with membrane dispersion(k=0.0349 min^-1).DMAc initial concentration(C0)and H202 flux (Jp)had major influence on mass transfer and kinetics,meanwhile,membrane pore size(rp)and length(L)also affected the Treaction rate.The intensifed radical yield,fast mass transfer and nanoparticles high activity all contributed to improve pollutant degradation eficiency.Time-resolved DMAC degradation pathway was analyzed as hydroxylation,demethylation and oxidation leading to the finai products of CO2;H20 and NO3^-(rather.than NH,from biodegradation).Continuous process was operated in the dual-membrane configuration with in situ reaction and separation.After five cycling,tests,DMAc removal was all above 95%for the initial[DMAc]0=14,000 mg/L in wastewater and stability of the catalyst and the membrane maintained weil.

Sol-Gel法制备Al_2O_3-SiO_2-TiO_2-ZrO_2复合陶瓷膜的研究

将Sol-Gel法应用于无机膜的制备,成功的研制出一种新型的膜面平整、膜厚均匀且无宏观缺陷的Al2O3-SiO2-TiO2-ZrO2复合陶瓷膜,复合膜含有γ-Al2O3、SiO2、TiO2、ZrO2和Al2SiO5等晶相,改变体系组成含量,晶相组成和含量随之变化,从而引起膜的显微结构的变化。利用XRD、SEM、AFM、EPMA等测试手段重点研究了膜的表面形貌和显微结构,并分析了添加剂、热处理方式等对膜的表面形貌和显微结构影响。

Sol-Gel法制备Al_2O_3-SiO_2-TiO_2-ZrO_2复合膜的结构研究

将Sol-gel法应用于无机膜的制备,成功地研制出一种新型的Al2O3-SiO2-TiO2-ZrO2复合陶瓷膜,膜面平整,无宏观缺陷,复合膜由-γAl2O3、TiO2和Al2SiO5等多相组成,改变体系组成,各相含量和主晶相也随之变化,从而影响到膜的微观结构。利用XRD、AFM、SEM分析重点研究了膜表面的微观形貌,并分析了掺杂物对膜表面性能的影响。

Fe_2O_3-Al_2O_3-SiO_2-TiO_2抗菌、纳米湿敏陶瓷薄膜的Sol-Gel制备

利用溶胶凝胶法制成了Fe2O3-Al2O3-SiO2-TiO2抗菌、纳米湿敏陶瓷薄膜。用扫描电镜和原子力显微镜对膜的表面形貌和显微结构进行表征,分析了处理方式对膜的表面形貌和微观结构的影响。制成的Fe2O3-Al2O3-SiO2-TiO2抗菌、纳米湿敏陶瓷薄膜具有广谱抗菌、高效、无毒、持久和耐热等特点。湿敏特性测试结果表明:Fe2O3-Al2O3-SiO2-TiO2抗菌、纳米陶瓷薄膜制品的感湿灵敏度高,具有较好的响应特性和稳定性。