Pervaporation performance and characterization of hydrophilic ZSM-5 zeolite membranes for high inorganic acid and inorganic salts

The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.

Pretreatment of Isopropanol Solution from Pharmaceutical Industry and Pervaporation Dehydration by NaA Zeolite Membranes

NaA zeolite membranes with 80 cm in length and 12.8 mm in outer diameter were prepared by our research group cooperating with Nanjing Jiusi Hi-Tech Co., China. The influence of dissolved inorganic salts and pH value in the feed of isopropanol （IPA） solution on NaA zeolite membranes was investigated. It was found that both factors exhibited strong influence on the stability of NaA zeolite membranes. A set of pretreatment steps such as pH adjustment and distillation of the IPA solution were proposed to improve stability for pervaporation dehydration. An industrial-scale pervaporation facility with 52 m2 membrane area was built to dehydrate IPA solution from industrial cephalosporin production. The facility was continuously operated at 368-378 K to dehydrate IPA solution from water mass content of 15%-20% to less than 2% with a feed flow rate of 400-500 L·h^-1 and an average water flux of 1-1.5 kg·m^-2·h-1. The successful application of this facility suggested a promising application of NaA zeolite mem-brane for IPA recovery from pharmaceutical production.

Modeling investigation of geometric size effect on pervaporation dehydration through scaled-up hollow fiber NaA zeolite membranes

A mass transfer model in consideration of multi-layer resistances through NaA zeolite membrane and lumen pressure drop in the permeate side was developed to describe pervaporation dehydration through scaled-up hollow fiber supported NaA zeolite membrane. It was found that the transfer resistance in the lumen of the permeate side is strongly related with geometric size of hollow fiber zeolite membrane, which could not he neglected. The effect of geometric size on pervaporation dehydration could be more significant under higher vacuum pressure in the permeate side. The transfer resistance in the lumen increases with the hollow fiber length but decreases with lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of d1/L （Rc） to achieve high permeation flux was empirically correlated with extraction pressure in the permeate side. Typically, for a hollow fiber supported NaA zeolite membrane with length of 0.40 m, the lumen diameter should be larger than 2.0 mm under the extraction pressure of 1500 Pa.

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.

Synthesis and Separation Performance of Y-type Zeolite Membranes by Pre-Seeding Using Electrophoresis Deposition Method

Y-type zeolite membranes were synthesized by a two-step approach in which a particle seed layer was prepared by electrophoresis deposition(EPD) at first, followed by densification through secondary growth. The pre-seeding adopted the directing agent for Y-type zeolite synthesis serving as seeds. The effects of aging time of the directing agent, electrophoresis voltage and electrophoresis deposition time on seed layers quality as well as the quality of zeolite membranes were investigated. The results indicated that the zeolite seeds derived from the directing agent could be evenly deposited on substrate under certain EPD conditions. The XRD patterns of the seeded substrates after the secondary growth showed that the pure as-synthesized Y-type zeolite membranes had successfully grown on the substrates. The SEM images indicated that the substrate was covered by the highly intergrown zeolite crystals when the seeding solution employed the directing agent with an aging time of 2 days. The separation performance of zeolite membrane was evaluated using a CO_2/N2 mixture(with a mole ratio of 1:1) at different temperatures. Furthermore, the pervaporation measurements were carried out for the dehydration of isopropanol aqueous solutions with different mass fractions. The as-synthesized Y-type zeolite membranes exhibited a relatively high selectivity of water from isopropanol and sustainable permeation flux.

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.

Enlarged Area A-type Zeolite Membranes Prepared by Vacuum Seeding Method

High quality A-type zeolite membranes, with enlarged area over 70 cm2, were successfully synthesized on a tubular a-Al2O3 support by applying the vacuum seeding method.

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.

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 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.

Evaluation of hollow fiber T-type zeolite membrane modules for ethanol dehydration

This work presents the design of hollow fiber T-type zeolite membrane modules with different geometric configurations. The module performances were evaluated by pervaporation dehydration of ethanol/water mixtures. Strong concentration polarization was found for the modules with big membrane bundles. The concentration polarization was enhanced at high temperature due to the higher water permeation flux. The increase of feed flow could improve water permeation flux for the membrane modules with small membrane bundle.Computational fluid dynamics was used to visualize the flow field distribution inside of the modules with different configurations. The membrane module with seven bundles exhibited highest separation efficiency due to the uniform distribution of flow rate. The packing density could be 10 times higher than that of the tubular membrane module. The hollow fiber membrane module exhibited good stability for ethanol dehydration.

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.

Synthesis and Separating Performance of SAPO-44 Zeolite Membrane

A defect-free SAPO-44 zeolite membrane firmly anchored the porous α-Al2O3 plate substrate was successfully synthesized. The separating results showed that the H2/N2 and H2/CO permselectivities were higher than those of the corresponding Knudsen diffusion and the substrate, attaining 5.78 and 7.15 respectively.

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.

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.

Growth mechanism of a preferentially oriented mordenite membrane

A preferentially oriented mordenite membrane was successfully prepared on a seeded porous α-alumina support. Characterization results of XRD (X-ray diffractometer) and FE-SEM (field emission scanning electron microscope) revealed that evolutionary selection might predominantly contribute to the formation of the sharply oriented mordenite membrane. The nec- essary conditions under which evolutionary selection occurs are: (a) the number density of nuclei on the support surface should be high enough at the early stage; (b) the crystals should grow fastest along one direction; and (c) the zeolite layer should proceed via the successive growth of the crystals nucleated on the support surface instead of the accumulation of the crystals formed in the bulk solution.

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.

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.