Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane

Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.

Synthesis of ZSM-5 zeolite membranes without organic templates using a varying-concentration technique

Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O∶100SiO2∶2Al2O3∶5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7, 3.27×10-7, 3.9×10-7, 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1, respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.

Growth process and short chain alcohol separation performance of fluoride-containing NaY zeolite membrane

Growth process of the NaY zeolite membranes was investigated by fluoride-containing precursor synthesis gel.Compared with the fluoride-free precursor synthesis gel,the irregular NaY zeolite crystals were dissolved into amorphous by the fluoride-containing precursor synthesis gel initially,the amorphous contained the Y-type zeolite characteristic bands by the IR characterization.The fine square NaY zeolite crystals arose from the amorphous,which were accumulated and gradually grew into a dense NaY zeolite layer on the support surface after 6.5 h.Because the excessive NaY zeolites were dissolved by the strong alkaline and fluoride-containing precursor synthesis gel,there was plenty of amorphous on NaY zeolites layer for prolonging the crystallization time.The assynthesized NaY zeolite membranes had a good separation performance and repeatability for separation of 10 wt%methanol(MeOH)/methyl methacrylate(MMA) mixture by pervaporation,the flux and separation factor were(1.27 ± 0.07) kg·M^(-2)·h^(-1) and(4900 ± 1500) at 323 K,respectively.Besides,the NaY zeolite membranes were applied to separate the other short chain alcohol from the various alcohol/organic ester and alcohol/organic ether mixtures,the NaY zeolite membranes showed high short chain alcohol perm-selectivity.

Synthesis of Compact NaA Zeolite Membrane by Microwave Heating Method

A continuous and dense NaA zeolite membrane was synthesized by microwave heating method while employing a multi-step seeding LTA zeolite with the average size of 120 nm. The gas H2/N2 mixture separating results indicated that the mixture selectivity increased with increasing of synthesis times. In addition, selectivity of the three-step synthesis was higher than the value(3.74) expected from Kundsen diffusion.

Preparation of Ferrierite Zeolite Membranes in the Absence of Organic Structure-directing Agents

Ferrierite zeolite membranes were prepared for the first time in the absence of organic structure-directing agents （SDA） on the surface of a porous a-alumina support. These membranes were characterized by means of X-ray diffraction （XRD）, scanning electron microscopy （SEM） and pervaporation tests.

Preparation of a novel composite electrode based on N-doped TiO_2-coated Na Y zeolite membrane and its photoelectrocatalytic performance

For the first time the preparation of the N-doped TiO2-coated NaY zeolite membrane（N-doped TiO2/NaY zeolite membrane） as an electrode material for photoelectrocatalysis has been achieved and reported.The XRD, SEM, UV–vis and XPS techniques were used to characterize the structure of the N-doped TiO2/NaY zeolite membrane. The results verified that the surface of the N-doped TiO2/NaY zeolite membrane was coated by TiO2 nanoparticles of ca. 20 nm size and exhibited a distinct red-shift in the UV–vis spectra compared to N-doped TiO2. The photoelectrocatalysis performance of the N-doped TiO2/NaY zeolite membrane electrode was evaluated by phenol degradation. The results revealed it is a promising novel electrode material for application of photoelectrocatalysis in the removal of organic contaminants in waste water.

Synthesis Optimization of SSZ-13 Zeolite Membranes by Dual Templates for N_(2)/NO_(2) Separation

High-silica SSZ-13 zeolite membranes are promising in industrial separations of light gases and continuous membranes are highly demanded for better separation performances. Herein, pure-phase, continuous and thin SSZ-13 zeolite membranes were synthesized using dual templates of N,N,N-trimethtyl-1-adamantammonium hydroxide(TMAdaOH) and tetraethylammonium hydroxide(TEAOH). Systematical investigations of TMAdaOH/TEAOH ratios and their concentrations show that TMAdaOH acts as the main structure-directing agent in the formation of the SSZ-13 zeolite. TMAdaOH cooperatively plays with TEAOH in promoting the SSZ-13 crystal intergrowth to form a continuous polycrystalline membrane. Additionally, appropriate introduction of TEAOH is able to adjust the membrane thickness to the crystal-comparable size of ca. 2.0 μm. The SSZ-13 membranes are further applied for N2/NO2separation, which is firstly reported on zeolite membranes. The gas permeation results show that the SSZ-13 membrane synthesized by the dual-template approach exhibits selective separation of N2 over NO2 with N2/NO2 separation factor of 7.6 and N2 permeance of 1.66×10-8 mol·m-2·s-1·Pa-1.

Preparation and permeability of ZSM-35 zeolite membranes on porous stainless steel tubes

ZSM-35 zeolite membranes were prepared on porous stainless steel tubes with silica sol and tetraethoxysi-lane as silica source,and with 1-butylamine and ethylenedi-amine as templates,respectively.The characterization of X-ray diffraction(XRD)and scanning electron microscopy(SEM)showed that the membranes prepared with ethylene-diamine as the template displayed growth orientation with their crystal planes(h00)parallel to the support surface.The single-component permeability tests of H2,N2 and C3H8 showed that the membranes synthesized with ethylene-diamine as the template,compared with those with 1-butylamine as the template,showed relatively higher permeation rates and ideal separation factors,and above their corresponding ideal Knudsen diffusion factors,which might be attributed to the different growth orientation of zeolite membranes synthesized with different templates.

Dual-templating surface gel into thin SSZ-13 zeolite membrane for fast selective hydrogen separation

Highly permeable zeolite membranes are desirable for fast gas separation in the industry.Reducing the membrane’s thickness is deemed to be an optimal solution for permeability improvement.Herein,we report the synthesis route of thin SSZ-13 zeolite membranes via the conversion of template-contained surface gels.The synthesis gel is fully crystallized into crack-free SSZ-13 membranes assisted with dual templates of N,N,N-trimethyl-1-adamantammonium hydroxide(TMAdaOH)and tetraethylammonium hydroxide(TEAOH).The specific functions of TMAdaOH for structure directing and TEAOH for crystallization regulating are well discussed.Thin surface gel layer is impregnated onto porous alumina with subsequent crystallization into a 500 nm thick membrane.This submicron-thick membrane exhibits high H_(2)permeance with 50×10^(-8)mol s^(-1)m^(-2)Pa^(-1)during hydrogen separation.Meanwhile,the separation factors are retained around 23.0 and 31.5 for H_(2)/C_(2)H_(6)and H_(2)/C_(3)H_(8),respectively.This approach offers a possibility for obtaining high-quality zeolite membranes for efficient hydrogen separation.

Improved SSZ-13 thin membranes fabricated by seeded-gel approach for efficient CO_(2) capture

High-quality standard oil synthetic zeolite-13(SSZ-13) membranes with thickness only ~ 1.0 μm were prepared on tubular supports by the new seeded-gel approach. Seeded-gel approach is simpler than the normal secondary-growth one since adding seeds in the gel is simpler than seeding on the support surface. The synthesis time was greatly reduced from 3.0 to 1.0 d after synthesis modification of gel aging and seed sizes. Low temperature ozone calcination was used for the removal of the organic structural directing agent. The best SSZ-13 membrane displayed CO_(2)permeances of 1.3 × 10^(-6) and 1.5 × 10^(-6) mol·m^(-2)·s^(-1)·Pa^(-1) and CO_(2)/CH_(4) and CO_(2)/N_(2) selectivities of 125 and 27 for equimolar CO_(2)/CH_(4) and CO_(2)/N2mixtures at 0.2 MPa pressure drop and 298 K, respectively. Separation performance of the membrane in the two binary mixtures is higher than that of most zeolite membranes. Three SSZ-13 membranes were reproducibly prepared on tubular supports by seeded-gel approach and the standard deviation ratios of CO_(2) permeance and CO_(2)/CH_(4) selectivity are 12.5% and 7%, respectively. It suggests that this new synthesis approach is creditable. The effects of temperature and pressure on separation performance of the thin SSZ-13 membranes were studied in the two binary mixtures. The tubular SSZ-13 membranes displayed great potentials for CO_(2) capture from natural gas, biogas and flue gas.

Adsorption dynamics of ethane from air in structured fixed beds with different microfibrous composites

Adsorption dynamics of ethane in two granular fixed beds and structured fixed beds with microfibrous composites was studied.5A zeolite membrane 5A/PSSF(paper-like sintered stainless steel fiber)and microfibrous entrapped activated carbon(MEAC)composites were prepared by wet layup papermaking/sintering technique and in-situ hydrothermal method.Microfibrous composites were characterized by X-ray diffraction,scanning electron microscopy and N2 adsorption/desorption.Structured fixed beds were designed by filling granular adsorbents(5A zeolite or activated carbon)and microfibrous composites at the inlet and outlet of the beds,respectively.Effects of flow rate,bed height and structure on the breakthrough curves were investigated.The length of unused bed(LUB)was determined,and Yoon–Nelson model was used to fit the breakthrough curves.The experimental results showed ethane was effectively adsorbed on the granular adsorbents and microfibrous composites.Both composites could decrease the LUB values and enhance bed utilization.All breakthrough curves fitted well to Yoon–Nelson model,with correlation coefficient exceeding 0.89.The adsorption rate of ethane could be improved in the structured fixed beds,which showed an enhanced mass transfer efficiency for ethane adsorption.LUB values of structured fixed beds with 5A/PSSF composites were larger,the bed utilization values were lower,and the adsorption rate constants were higher than those with MEAC composites under the same conditions.

Factors affecting the formation of zeolite seed layers and the effects of seed layers on the growth of zeolite silicalite-1 membranes

The present study investigates the formation of silicalite-1 seed layers on a porous carbon support of 0.5µm pore size andα-Al_(2)O_(3) supports with different pore sizes(0.1µm and 4µm)via the slip-casting technique.The effects of support property,seed size and solvent on the formation of seed layers were investigated in detail.The growth of sili-calite-1 membranes on different seeded supports by hydro-thermal synthesis was also evaluated.The scanning electron microscopy(SEM)and X-ray diffraction(XRD)character-izations indicate that a continuous seed layer can be obtained on the smooth support of 0.1µm pore size by using any seed of 100 nm,600 nm or 2.2µm in size,whereas,on the coarse supports with either 0.5µm or 4µm pore size,a continuous seed layer cannot be formed using the above seed sizes and the same seeding time.At a longer contact time,a seed layer can also be formed using 100 nm seed on the supports with larger pore size.However,the layer is not uniform and smooth.For a hydrophobic porous carbon support,seeding ethanol suspension,which has weak polarity,favors the formation of a continuous seed layer.The seed layers and membranes grown from the smaller seed are more uniform and continu-ous and possess smoother surfaces than those from the larger seed.The seed layer and respective grown membrane formed from nanosized seed(100 nm)are the most uniform and compact.With this method of seeded secondary synthesis of zeolite membranes,the quality of a membrane mainly depends on the quality of the seed layer.

Mixed Matrix Membranes of Polysulfone/Polyimide Reinforced with Modified Zeolite Based Filler: Preparation, Properties and Application

In this work, polysulfone/polyimide（PSf/PI） mixed matrix membranes were fabricated by reinforcement of modified zeolite（MZ） particles through solution casting method for investigation of antibacterial activity against two gram negative bacteria（Salmonella typhi, Klebsella pneumonia） and two gram positive bacteria（Staphylococcus aureus, Bacillus subtilis）. The modified zeolite particles were incorporated to PSf and PI matrix and the influence of these particles on thermal, mechanical and structural properties was evaluated. The morphological evolution was investigated through scanning electron microscopy（SEM） and transmission electron microscopy（TEM） analysis, which revealed good compatibility between organic polymer matrix and inorganic filler. Mechanical stability was investigated by tensile testing while thermal analysis was evaluated by thermogravimetric analysis（TGA） and differential scanning calorimetry（DSC）. This revealed improvement in thermal properties with increasing filler concentration from 1 wt% to 10 wt%. Structural analysis was successfully done using X-ray diffraction analysis（XRD） and Fourier transform infrared（FTIR） spectroscopy. Solvent content of fabricated mixed matrix membranes was observed to decrease while moving from more hydrophilic to less hydrophilic solvent. However, addition of filler content enhanced the porosity of fabricated membranes. The synthesized mixed matrix membranes exhibited good antibacterial activity and the highest activity was shown by PSf/PI/MZ mixed matrix membrane. Therefore, the combination effect of PSf, PI and MZ sufficiently enhanced the antibacterial activity of mixed matrix membranes.

Preferential Oxidation of CO in a Hydrogen-Rich Gas Through Au/NaY Catalytic Membranes

This paper describes novel Au/NaY catalytic membranes for preferential oxidation of CO （CO-PROX） in an H2-rich gas. NaY zeolite membranes with a high CO2/N2 separation factor were loaded with nanosized Au particles using an ion-exchanged method. X-ray diffraction analyses showed that the structure of the NaY zeolite was not damaged by the ion exchange process. CO-PROX experiments showed that the catalytic membranes had excellent catalytic performance for selective oxidation of CO. The CO/H2 molar ratio on the permeate side decreased with increasing operating temperature in the range of 80-200℃. At 200℃, almost no CO was detected from the permeate stream of a catalytic membrane with the feed con- taining 0.67% CO, 1.33% 02, 32.67% H2, and He in balance. Thus, these Au/NaY catalytic membranes show a promise for CO removal from hydrogen fuels.

Inorganic microporous membranes for hydrogen separation:Challenges and solutions

Porous membrane separation is a competitive hydrogen purification technology due to the advantages of environmental friendliness,energy-saving,simple operation,and low cost.Benefiting from the booming development of materials science and chemical science,great progress has been made in H_(2) separation with porous membranes.This review focuses on the latest advances in the design and fabrication of H_(2) separation inorganic microporous membranes,with emphasis on the synthetic strategies to achieve structural integrity,continuity and stability.This review starts with a brief introduction to the membrane separation mechanisms,followed by an elaboration on the synthetic challenges and corresponding solutions of various high-performance inorganic microporous membranes based on zeolites,silica,carbon,and metal-organic frameworks(MOFs).At last,by highlighting the prospects of ultrathin two-dimensional(2D)porous membranes,we wish to shed some light on the further development of new materials and membranes for highly efficient hydrogen separation.

Facile preparation of compact LTA molecular sieve membranes on polyethyleneimine modified substrates

A facile preparation strategy was proposed for preparation of compact zeolite LTA membranes on polyethyleneimine(PEI)modified substrates without seeding.Through the functionalization of substrates by using PEI,compact LTA membranes can be formed on various kinds of substrates.A well-intergrown and phase-pure LTA membrane with a thickness of about 3.0μm is successfully prepared on the a-Al_(2)O_(3)disk after crystallization for 24 h at 60℃.Besides LTA membrane,wellintergrown zeolite FAU membranes can also be formed on PEI-modified a-Al_(2)O_(3)substrates,suggesting the universality of this strategy.The zeolite LTA membranes synthesized on PEI-modified a-Al_(2)O_(3)tubes were evaluated for the separation of alcohols/water mixture through pervaporation.The as-synthesized zeolite LTA membranes display high pervaporation performances.For the separation of 10 wt%isopropanol/water solution at 90℃,a high separation factor of44991 and a water flux of 1.73 kg m^(-2)h^(-1)are achieved.