Reverse osmosis of diluted skim milk: Comparison of results obtained from vibratory and rotating disk modules

This paper investigates the reduction of ionic concentration and carbon oxygen demand (COD) in dairy process waters modelled by one volume of skim milk diluted with two volumes of water using shear-enhanced reverse osmosis. Initial COD and conductivity were, respectively, 36,000 mg O₂ L⁻¹ and 2000 μS cm⁻¹. We have compared the performances of a VSEP vibratory pilot and of a single rotating disk-stationary membrane module equipped with the same Desal AG membrane (Osmonics). Membrane shear rates were varied by changing the vibration frequency in the VSEP and the disk rotation speed or adding radial vanes in the other module. In all tests the permeate COD was reduced below 15 mg O₂ L⁻¹. Permeate fluxes reached a maximum of 180 L h⁻¹ m⁻² at a transmembrane pressure (TMP) of 4 MPa at initial concentration with the VSEP at its resonant frequency and with the disk equipped with 6 mm high vanes rotating at 2000 rpm. Permeate conductivity fell from 60 μS cm⁻¹ at 1 MPa to about 18 μS cm⁻¹ at 4 MPa. In concentration tests, corresponding permeate fluxes at the maximum volume reduction ratio reached (VRR = 8), were 55 L h⁻¹ m⁻² for the VSEP and 60 L h⁻¹ m⁻² for the rotating disk at a TMP of 4 MPa. Permeate conductivities increased exponentially with VRR from 18 to 210 μS cm⁻¹ for the rotating disk and to 250 μS cm⁻¹ for the VSEP. However the mean conductivity of collected permeate varied from 38 μS cm⁻¹at highest shear rate to 60 at lower shear rates. This study shows that these filtration systems permit to obtain reusable water from this high initial COD model effluent with one single reverse osmosis step.     

Elimination of organic matter present in wastewaters from the cork industry by membrane filtration

BACKGROUND: The first stage of the cork industrial process generates great volumes of wastewater with moderate to high organic pollutant content that must be purified using different procedures, such as filtration by membranes. RESULTS: The tangential filtration of these wastewaters was studied using two different laboratory equipments. In the first one, three ultrafiltration (UF) membranes were tested, with molecular weight cut‐off (MWCO) 100 kDa and 30 kDa, and two operating modes were used: total recycling of permeate and retentate streams, and in continuous mode, without recycling both streams. In the total recycling UF experiments, the influence of the operating variables on the permeate flux was first established. The effectiveness of the different membranes was determined by evaluating the rejection coefficients for several parameters that measure the global pollutant content of the effluent. The values found for these rejection coefficients were in the following order: ellagic acid and color > absorbance at 254 nm > tannic content > COD (chemical oxygen demand). In the continuous mode experiments, the fouling mechanism for each membrane was established by fitting the experimental data to various filtration fouling models given in the literature. The operating mode in the second equipment was batch concentration, and additional experiments were carried out with an UF membrane (2 kDa), and with a NF membrane (with MWCO in the range 150–300 Da). CONCLUSIONS: The three operating modes tested provided different rejection levels of organic matter; among them, the most effective procedure tested was batch concentration mode using a NF membrane. Copyright © 2007 Society of Chemical Industry     

Preparation of zeolite NaA membranes on the inner side of tubular supports by means of a controlled seeding technique

Zeolite NaA membranes have been reproducibly prepared by seeded hydrothermal synthesis on the internal surface of porous -alumina tubular supports. A cross-flow filtration technique has been developed to allow a controlled seeding of zeolite NaA crystals from a suspension according to transmembrane pressure, pH, seed suspension flow rate, crystal size and concentration. The optimal seeding weight gain was found to be around 0.40 mg cm⁻² of membrane area. With this procedure, zeolite membranes with selectivities up to 600 at fluxes of 0.50 kg m⁻² h⁻¹ were obtained in the pervaporation of 92:8 wt.% ethanol/water mixtures at 323 K.     

Activity, selectivity and durability of VO–ZSM-5 catalysts for the selective catalytic reduction of NO by ammonia

ZSM-5 zeolite was loaded with vanadyl ions (VO²⁺) by treatment of Na–ZSM-5 with aqueous VOSO₄ solution at pH 1.5–2. The catalytic material was tested for the selective catalytic reduction of NO with ammonia at temperatures between 473 and 823 K and normal pressure using a feed of 1000 ppm NO, 1000 (or 1100) ppm NH₃ and 2% O₂ in He. The catalyst proved to be highly active, providing, e.g. initial NO conversions of >90% at 620 l g⁻¹ h⁻¹ (≈400 000 h⁻¹) and 723 K, and selective, providing nitrogen yields equal to NO conversion at equimolar feed in a wide temperature range and only minor N₂O formation at NH₃ excess. Admixture of SO₂ (200 ppm) resulted in an upward shift of the useful temperature range, but did not affect the catalytic behaviour at temperatures ≥623 K. No SO₂ conversion was noted at T ≤ 723 K and 450 l g⁻¹ h⁻¹. The poisoning effect of water (up to 4.5 vol%) was weak at temperatures between 623 and 773 K. VO-ZSM-5 catalysts are gradually deactivated already under dry conditions, probably by oxidation of the vanadyl ions into pentavalent V species. This deactivation is considerably accelerated in the presence of water.     

High flux mesoporous MCM-48 membranes: Effects of support and synthesis conditions on membrane permeance and quality

This communication reports experimental efforts to synthesize defect-free mesoporous MCM-48 membranes with improved gas flux. We demonstrate a facile and inexpensive method of synthesizing defect-free supported MCM-48 membranes with improved N₂ and CO₂ permeance (>2 × 10⁻⁷ mol/m² s Pa) employing asymmetric supports for the membrane synthesis which contain layers of macropores possessing different pore sizes. The membranes prepared on asymmetric -alumina supports displayed higher gas permeance than those fabricated on symmetric supports (N₂ permeance <10⁻⁷ mol/m² s Pa) as confirmed by unsteady-state gas permeation experiments. Further improvement in gas permeance was achieved by covering one face and the sides of the support with a ceramic tape during membrane synthesis.     

Selective permeation and separation of steam from water–methanol–hydrogen gas mixtures through mordenite membrane

Separation properties of a mordenite membrane for water–methanol–hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49–156 and 73–101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹ up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 503 K and reached to 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol.     

Influence of exchanged cations (Na, Cs, Sr and Ba) on xylene permeation through ZSM-5/SS tubular membranes

Na-ZSM-5 membranes were synthesized by secondary growth on the outer surface of stainless steel porous tubes. The membranes were ion-exchanged with Cs⁺, Ba²⁺ and Sr²⁺ to investigate their effect upon the separation of p-xylene from m-xylene and o-xylene. The permeation through the membranes was measured between 150 and 400 °C using each xylene isomer separately and a ternary mixture. All the membranes were selective to p-xylene in the temperature range studied. N₂ and xylene permeation measurements together with SEM observations were used to determine whether or not cracks and/or pinholes developed after exposure to the xylene isomers at high temperature (400 °C). Neither pore blockage nor extra-zeolitic pores developed after the ion exchange procedure and subsequent calcination. Furthermore, duplicate synthesized membranes of each cation form had similar separation factors and permeances. The duplicate values differ much less than the measurement error. The p-xylene permeation flux decreased in the order: Na-ZSM-5 > Ba-ZSM-5 > Sr-ZSM-5  Cs-ZSM-5 while the permeation flux of the m- and o-xylene decreased in the order Na-ZSM-5 > Sr-ZSM-5 > Ba-ZSM-5 > Cs-ZSM-5. The membrane that exhibited the best performance was Ba-ZSM-5, with a maximum p/o separation factor of 8.4 and a p-xylene permeance of 0.54 × 10⁻⁷ mol s⁻¹ m⁻² Pa⁻¹ at 400 °C.     

Kinetics of resid hydrotreating reactions

Five resids from the Middle East and China have been hydrotreated in a pilot plant, which has three fixed-bed reactors in series. Six commercial catalysts were tested. The process conditions were 12.0–16.8 MPa, 370–405°C, LHSV of 0.15–1.0 h⁻¹, H₂/oil ratio of 400–1000 nm³ m⁻³. The feedstocks included the following Chinese resids Shengli, Xinjiang and Liaohe. Kinetic parameters of resid hydrotreating reactions were calculated in terms of pore diffusion resistance and were correlated with some special properties of oils and catalysts. This study supplies important basic data for the selection of catalysts, for the design of composite catalyst beds and for the optimization of process conditions.     

Microwave-enhanced catalytic degradation of phenol over nickel oxide

A mix-valenced nickel oxide, NiO_x, was prepared from nickel nitrate aqueous solution through a precipitation with sodium hydroxide and an oxidation by sodium hypochlorite. Further, pure nickel oxide was obtained from the NiO_x by calcination at 300, 400 and 500 °C (labeled as C300, C400 and C500, respectively). They were characterized by thermogravimetry (TG), X-ray diffraction (XRD), nitrogen adsorption at −196 °C and temperature-programmed reduction (TPR). Their catalytic activities towards the degradation of phenol were further studied under continuous bubbling of air through the liquid phase. Also, the effects of pH, temperature and kinds of nickel oxide on the efficiency of the microwave-enhance catalytic degradation (MECD) of phenol have been investigated. The results indicated that the relative activity affected significantly with the oxidation state of nickel, surface area and surface acidity of nickel oxide, i.e., NiO_x (>+2 and S_BET = 201 m² g⁻¹)  C300 (+2 and S_BET = 104 m² g⁻¹) > C400 (+2 and S_BET = 52 m² g⁻¹) > C500 (+2 and S_BET = 27 m² g⁻¹). The introduction of microwave irradiation could greatly shorten the time of phenol degradation.     

On-stream modification of MFI zeolite membranes for enhancing hydrogen separation at high temperature

-Alumina-supported MFI zeolite membranes were modified by on-stream catalytic thermal cracking of methyldiethoxysilane (MDES) molecules inside the zeolitic channels during the separation of H₂/CO₂ gas mixture at 450 °C and atmospheric pressure. The MDES vapor was carried by the H₂/CO₂ feed gas and the effect of modification was monitored continuously through online analysis of the permeate stream. The modified membrane exhibited a significant increase in H₂ selectivity over CO₂ with a moderate decrease in H₂ permeance. At 450 °C, the modified MFI membrane obtained a H₂/CO₂ permselectivity of 17.5 with H₂ single gas permeance of 1.86 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ as compared to a permselectivity of 2.78 and permeance of 2.75 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ for the membrane before modification. The modified membrane also showed good performance and stability in separation of H₂/CO₂ gas mixture containing up to 28.4% water vapor at 450 °C and atmospheric pressure.     

Electrochemical removal of antibiotics from wastewaters

Electro-oxidation tests with different anodes (Ti/Pt, DSA^® type, graphite and three-dimensional (3D) electrode made of a fixed bed of activated carbon pellets) were performed on aqueous solutions containing the antibiotics Ofloxacin and Lincomycin. The effectiveness of the treatment of wastewater containing pharmaceuticals was assessed, as well as the electro-oxidation mechanism.

The use of high electrode potentials (>2.8 V versus NHE) ensured either significant anodic surface activation or minimization of fouling by in situ generated polymeric material. The use of a membrane-divided cell showed positive aspects in terms of molecule demolition, and average power consumption. The electro-oxidation was found to occur with first order kinetics mainly at anode surface when using Na₂SO₄ at low concentration (0.02N). Under these conditions, Ofloxacin is efficiently oxidized over all tested anodes (e.g. 50 mgcm⁻² A⁻¹ h⁻¹ for the bi-dimensional Ti/Pt electrode), whereas Lincomycin is oxidized with slow overall kinetics mainly due to difficult deprotonation, a step that precedes the primary electron transfer stage of the oxidation process. The three-dimensional electrode would be the most appropriate for continuous industrial-scale process. However, at the used potential, unacceptable corrosion of the carbon based electrode was noticed.     

Partial oxidation of methane in Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor at high pressures

Oxygen permeation fluxes through dense disk-shaped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) membranes were investigated as a function of temperature (973–1123 K), pressure (2–10 atm), and membrane thickness (1–2 mm) under an air/helium gradient. A high oxygen permeation flux of 2.01 ml/cm² min was achieved at 1123 K and 10 atm under an air/He oxygen partial pressure gradient. Based on the dependence of the oxygen permeation flux on the oxygen partial pressure difference across the membrane and the membrane thickness, it is assumed that bulk diffusion of oxygen ions was the rate-controlling step in the oxygen transport across the BSCFO membrane disk under an air/He gradient. The partial oxidation of methane (POM) to syngas using LiLaNiO_x/γ-Al₂O₃ as catalyst in a BSCFO membrane reactor was successfully performed at high pressure (5 atm). Ninety-two percent methane conversion, 90% CO selectivity, and 15.5 ml/cm² min oxygen permeation flux were achieved in steady state at a temperature of 1123 K and a pressure of 5 atm. A syngas production rate of 79 ml/cm² min was obtained. Characterization of the membrane surface by SEM and XRD after reaction showed that the surface exposed to the air side preserved the Perovskite structure while the surface exposed to the reaction side was eroded.     

Sorption kinetics of ammonia and ammonium ions on gel and macroporous sulphonic acid cation exchangers

Diffusion of ammonia and ammonium ions in sulphonic acid cation exchangers (gel Purolite SGC 100 × 10 MBH and macroporous Purolite C 160 MBH) from the solutions, representing the composition of “caustic condensate” (waste of nitrogen fertilizers production) is affected by pH of initial solution and structure of the matrix of cation exchanger. In gel matrix the effective intraparticle diffusivity (D_ef) depends greatly on the solution pH because of shrinkage in alkaline and swelling in acidic medium: on decreasing the initial concentration of ammonia from 0.214 to 0.003 and increasing that of ammonium nitrate from 0 to 0.214 mol l⁻¹ instead, the effect of ion exchange leads to a decrease in pH, resulting in swelling and increase in D_ef from 0.1 to 0.34 × 10⁻¹⁰ for gel Purolite SGC 100 × 10 MBH and variation of 0.18–0.11 × 10⁻¹⁰ m² s⁻¹ for macroporous Purolite C 160 MBH (resistant to shrinkage and swelling).

In Purolite C 160 MBH both macropore diffusivity (0.07–0.29 × 10⁻¹⁰ m² s⁻¹) and gel (solid phase) diffusivity (0.06–0.19 × 10⁻¹⁰ m² s⁻¹) are higher than micropore diffusivity (0.28–0.56 × 10⁻¹⁸ m² s⁻¹).

With respect to the effective intraparticle diffusivity, resistance to nitric acid, used for the regeneration, and high concentration of ammonium nitrate in eluate (up to 110 g l⁻¹), Purolite C 160 MBH has been installed for the conversion of ammonia and ammonium ions to ammonium nitrate reusable in the fertilizers production. This allows minimizing the economic loss and preventing the environmental contamination.     

D-tracer study of butadiene hydrogenation and tetrahydrothiophen hydrodesulphurisation catalysed by Co9S8

H₂/D₂ exchange (473–583 K), 1,3-butadiene hydrogenation (418–513 K) and tetrahydrothiophen hydrodesulphurisation (428–557 K) have been studied over powdered Co₉S₈ (surface area, 7 m² g⁻¹) using D₂ as an isotopic tracer. Hydrogen exchange proceeded as a first order process at a modest rate (k₅₄₀ = 1.0 h⁻¹ m⁻²) with an apparent activation energy of 67 kJ mol⁻¹. Butadiene hydrogenation was diagnostic as to the surface state of Co₉S₈; samples showed either predominant 1:2-addition or 1:4-addition of hydrogen, interpreted as indicating the presence in the surface of single sites or pair/ensemble sites, respectively. Reactions at 473 K in the presence of D₂ gave butenes containing 0–6 D-atoms: exchange patterns obtained from these D-distributions showed that a proportion of butadiene molecules underwent extensive dehydrogenation during the normal progress of hydrogenation. At 633 K this dehydrogenation activity was evident as self-hydrogenation which occurred in the absence of D₂. Tetrahydrothiophen was desulphurised in the presence of D₂ to thiophen (void of D), butadiene (containing 0–5 D-atoms) and 1-butene (containing mostly 0 and 4 D-atoms). Increase in temperature or in deuterium pressure favoured butene formation so that it became the dominant product (88%). Tetrahydrothiophen also underwent self-hydrodesulphurisation in the absence of D₂. A mechanism is proposed, consistent with this D-tracer information, that accommodates dehydrogenation, desulphurisation and hydrogenation steps in the overall process. The activity of powdered Co₉S₈ exceeded that of powdered MoS₂.     

AMnO3 (A=La, Nd, Sm) and Sm1−xSrxMnO3 perovskites as combustion catalysts: structural, redox and catalytic properties

Catalytic combustion of methane has been investigated over AMnO₃ (A = La, Nd, Sm) and Sm_1−xSr_xMnO₃ (x = 0.1, 0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space velocity = 40 000 N cm³ g⁻¹ h⁻¹, CH₄ concentration = 0.4% v/v, O₂ concentration = 10% v/v.

Specific surface areas of perovskites were in the range 13–20 m² g⁻¹. XRD analysis showed that LaMnO₃, NdMnO₃, SmMnO₃ and Sm_1−xSr_xMnO₃ (x = 0.1) are single phase perovskite type oxides. Traces of Sm₂O₃ besides the perovskite phase were detected in the Sm_1−xSr_xMnO₃ catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant fraction of Mn(IV) in AMnO₃. The fraction of Mn(IV) in the Sm_1−xSr_xMnO₃ samples increased with x. TPR measurements on AMnO₃ showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III) and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO₃ > NdMnO₃ > SmMnO₃. In Sm_1−xSr_xMnO₃ the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature. Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO₂ below 1023 K. The activation energies of the AMnO₃ perovskites varied in the same order as the onset temperatures in TPR experiments suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO₃ perovskites resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism.     

Synthesis and oxygen transport characteristics of dense and porous cerium/gadolinium oxide materials: Interest in membrane reactors

Cerium/gadolinium oxide (CGO)-based ceramic ion conductive membranes (CICMs) have potential uses in catalytic membrane reactors (CMRs) and solid oxide fuel cells (SOFCs). A supercritical CO₂ aided sol–gel process allowed the synthesis of CGO materials with the composition Ce_0.9Gd_0.1O_1.95. The produced nanophase powders were non-agglomerated, with a controlled morphology, a high purity and a high specific surface area (>100 m²/g). The CGO cubic crystalline phase has been obtained at temperatures <300 °C, lower than those of conventional solid state chemistry routes. With respect to ionic oxygen transport, a high conductivity at intermediate temperature (2 × 10⁻² S cm⁻¹ at 600 °C), almost equivalent in dense and porous samples, has been obtained on sintered materials prepared from these powders. In relation to their porosity characteristics, a modelling approach successfully explained the high ionic oxygen transport of some specific porous samples. Future directions for preparing porous conductive ceramics well adapted to CMR or SOFC applications can be anticipated from this model.     

Dechlorination kinetics of monochlorobiphenyls by Fe/Pd: Effects of solvent, temperature, and PCB concentration

Well-known, yet undefined, changes in the conditions and activity of palladized zerovalent iron (Fe/Pd) over an extended period of time hindered a careful study of dechlorination kinetics in long-term experiments. A short-term experimental method was, therefore, developed to study the effects of temperature and solvent on the dechlorination of monochlorobiphenyls (MCBs), 2-chlorobiphenyl (2-ClBP), in particular by Fe/Pd. The experiments started with specified initial conditions and lasted only for 10 min. The average value (k) of the first-order rate constant for the dechlorination of 2-ClBP was 0.13 ± 0.03 L m⁻² h⁻¹, not significantly different from the average values for 3-chlorobiphenyl and 4-chlorobiphenyl. The apparent activation energy was 20 ± 4 kJ mol⁻¹ and 17 ± 7 kJ mol⁻¹, in a temperature range between 4 °C and 60 °C, for the dechlorination of 2-ClBP using two batches of Fe/Pd catalyst. The k values decreased significantly in mixtures with a methanol concentration higher than 10%. The values of the rate constant were slightly influenced by the initial concentrations in the experiments at a low temperature and in a solution with a high methanol concentration. The concentration dependence was described with a Langmuir equation, based on the Langmuir–Hinshelwood mechanism that includes an adsorption step of a single species preceding a rate-determining catalytic reaction.     

Water/ethanol permeation properties through poly(hydroxymethylene) and poly(hydroxymethylene-co-fluoroolefin) membrane by pervaporation method

Poly(hydroxymethylene) and poly(hydroxymethylene-co-fluoroolefin) membranes were prepared utilizing highly purified vinylenecarbonate monomer. Molecular structure of these polymers was studied by NMR spectroscopy. Permeation characteristics of these membranes toward water/ethanol mixtures were investigated by pervaporation. The permeation rate of the polymer membrane (thickness:30–60μm) was in the range of Q=0.001–0.3 kg·⁻²·h⁻¹, and it gave a separation factor greater than 1000.     

Reduction of nitrite by sulfamic acid and sodium azide from aqueous solutions treated by gliding arc discharge

Nitrous and nitric acids form in aqueous solutions exposed to a gliding arc discharge burning in humid air. The anions interfere when the concentration of particular solutes such as pollutants must be determined. In particular they falsify the COD measurements and spectral investigations and thus the efficiency of the plasma treatment in pollutant abatement. The nitrite anions must be thus removed, which require specific reagents. The influence of parameters such as solution pH and [reducers]/[NO₂⁻] ratio on the reduction reaction was evaluated. The reduction of nitrite into N₂ either by sulfamic acid or sodium azide is a first-order pH-dependant reaction with regard to nitrite and reducers (k₁ = 2.93 × 10⁻¹ m³ kmol⁻¹ s⁻¹; k₂ = 6.21 × 10⁻¹ m³ kmol⁻¹ s⁻¹, respectively). Sodium azide is thus more reactive than sulfamic acid.