Electrochemical removal of cadmium using a batch undivided reactor with a rotating cylinder electrode

The performance of an undivided electrochemical batch reactor with a rotating cylinder electrode under potentiostatic control is examined for the removal of cadmium from a sodium sulfate solution containing 500ppm Cd(II) at pH ≅ 7. The effect of hydrogen evolution as a side cathodic reaction on the figures of merit of the reactor is analysed. The best results were obtained for a cathode potential of -0.9 V against the saturated calomel electrode. With an angular velocity of 1500rpm the space time yield and the normalized space velocity were 0.66 mol m-3s-1 and 3.9 h-1 respectively, while the fractional conversion was 67.3% with a current efficiency of 66.7%. The surface morphology of the deposits as a function of the applied potential is also reported. © 2001 Society of Chemical Industry.Fil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Bisang, Jose Maria. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin

Removal of cadmium and production of cadmium powder using a continuous undivided electrochemical reactor with a rotating cylinder electrode

The behaviour of a continuous undivided electrochemical reactor with a rotating cylinder electrode under potentiostatic control is examined for the abatement of cadmium from synthetic sodium sulfate solutions with Cd(II) concentrations lower than 500 mgdm-3 at a reactor inlet pH ≅ 7. The process was designed to convert the metal ions in solution to metal powder, which settles to the conical of the reactor and may be removed at intervals as a sludge by opening a drop valve. The effect of applied potential, inlet cadmium concentration, rotation speed and hydrogen evolution as side cathodic reaction on the 'figures of merit' of the reactor are analysed. The best results were obtained for cathode potentials in the range from -0.9V to -1.0V against the saturated calomel electrode. Therefore, when the rotation speed was 1000rpm the space time yield and the normalized space velocity were 0.64 × 10-2 mol m-3s-1 and 0.89h-1 respectively, while the fractional conversion per pass was 35% with a current efficiency higher than 74%. The surface morphology of the deposits as a function of the process variables is also reported. © 2002 Society of Chemical Industry.Fil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Bisang, Jose Maria. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin

Hydrocracking of long paraffins over Pt-Pd/WO3-ZrO2 in the presence of sulfur and aromatic impurities

The hydrocracking of long paraffins in the presence of sulfur and aromatic impurities using Pt–Pd/WO3–ZrO2 was assessed. The catalysts were tested for n-hexadecane hydrocraking in the presence and absence of several poisons, benzothiophene, quinolein, carbon disulfide, benzene, and naphthalene. At small impurity levels, aromatics are beneficial for the hydrocracking of long paraffins because they increase the liquid yield and reduce the cracking to light gases. Sulfur compounds were strong poisons of the activity. Benzothiophene was the strongest, producing the highest decline in activity and being more strongly chemisorbed than basic quinolein. Sulfur poisoning drastically affected the hydrocracking activity, indicating that acid isomerization cracking on WO3–ZrO2 follows a bifunctional mechanism with a big influence of the metal function. Incorporation of Pd to Pt/WO3–ZrO2 reduced the sulfur poisoning, with Pt–Pd (3:1)/WO3–ZrO2 being the best catalyst for stable hydrocracking of long paraffins in the presence of sulfur. This catalyst retained most of the activity of the Pt/WO3–ZrO2 parent material while being less affected by sulfur.Fil: Busto, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Sepulveda, Jorge H.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Tsendra, Oksana. National Academy of Sciences. Chuiko Institute of Surface Chemistry; UcraniaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Preventing self-poisoning in [Pt/Al2O3 + SO42−-ZrO2] mixed catalysts for isomerization-cracking of heavy alkanes by prereduction of the acid function

The activity and stability of composite catalysts obtained by mixing Pt/Al2O3 with SO42−-ZrO2, were studied in the reaction of hydroisomerization-cracking of n-octane (300 °C, 1.5 MPa, WHSV=4 h−1, H2/n-C8=6) obtaining light isoalkanes (isobutane, isopentane, isohexane), very important components of the pool of reformulated gasoline. Both components of the composites were pretreated in H2 before mixing. Prereduction eliminated the fraction of SO42− reducible at low temperature, thought to produce SO2 during reaction, a poison for the metal function. A reduction in the poisoning of the metal, produced by adsorption of S compounds, was tried in order to get a higher metal activity for the production of atomic H, needed for the hydrogenation of coke precursors and the prevention of deactivation. The pretreatment temperature was adjusted between 300 and 500 °C in order to keep a suitable amount of sulfate, needed for a sustainable isomerizing-cracking activity and for the stabilization of the tetragonal crystal phase of ZrO2, the most catalytically active crystal phase. When compared to non-reduced catalysts, composites reduced at 300–350 °C displayed improved activity and stability for benzene hydrogenation, a metal-catalyzed reaction, and the results were addressed to a decrease in S poisoning. In the pretreated composites the SO42−-ZrO2 active tetragonal phase was maintained in spite of the loss of S. For isomerization-cracking of n-octane, the pretreated catalysts showed a higher selectivity to isobutane and a fairly longer stability than non-pretreated catalysts, like Pt/SO42−-ZrO2 and SO42−-ZrO2 mixed with Pt/Al. TPO tests showed that the catalysts were essentially free of coke. This fact was addressed to a lower coking rate on prereduced sites and to a higher metal activity for hydrogenation of coke precursors.Fil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Parera, Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Surface characterization and dehydrocyclization activity of Pt/KL catalysts prepared by different methods

Three Pt/KL-zeolite catalysts containing 1 wt.% of metal were prepared by different procedures: CI-1 and CI-2 by wetness impregnation of the zeolite with aqueous solutions of Pt(NH3)4(OH)2 and Pt(NH3)4(NO3)2, respectively, and CE-3 by ion exchange with a Pt(NH3)4(OH)2 solution. These samples were successively calcined at 573 K and reduced at 773 K. An additional sample, CE-3-n, was obtained from CE-3 by ion-exchange with KNO3. The catalysts were characterized by H2–O2 titration, TPD of NH3, XRD, CO–FTIR and XPS and tested in the dehydrocyclization of n-heptane to toluene at 723 K, 100 kPa, WHSV=3.4 h−1 and H2/nC7=7.3 mol mol−1 in a fixed bed tubular reactor. Characterization results show that Pt dispersion for the ion exchanged samples is higher than for the impregnated ones and CE-3 is the more acidic catalyst. FTIR measurements indicate that the highest population of electron reach platinum species (Ptδ−) is found in CE-3-n, while CE-3 exhibits the highest concentration of electron deficient platinum species (Ptδ+). The order of dehydrocyclization activity, CE-3-n>CI-2>CI-1>CE-3, roughly correlates with that of the intensity of the FTIR bands attributed to Ptδ−. The low selectivity toward toluene of CE-3 is attributed to the protons generated during the reduction of Pt2+ exchanged.Fil: Arcoya, Adolfo. Instituto de Catálisis y Petroleoquı́mica (CSIC); EspañaFil: Seoane, Xosé Lois. Instituto de Catálisis y Petroleoquı́mica (CSIC); EspañaFil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Hydroisomerization–cracking of n-octane on Pt/WO42−–ZrO2 and Pt/SO42−–ZrO2: Effect of Pt load on catalyst performance

The hydroconversion (isomerization–cracking) of n-octane was studied at 300°C, 1.5 MPa, WHSV=4 and H2/nC8=6 using oxoanion promoted zirconia with different Pt concentrations (0.1, 0.5 and 1%) as catalysts. Tungstate was added to zirconia by impregnation with ammonium meta-tungstate or tungstic acid solutions and calcined at 800°C. Sulfate was added by impregnation with 2N H2SO4 and calcined at 620°C. Isooctanes are intermediate products that are cracked to C3–C5 alkanes with predominance of isoalkanes. Sulfate zirconia is the most active and selective catalyst to cracking products. The addition of 0.1% of Pt produces an increase in activity and stability, respect of the support without metal. However, the increase in Pt content (0.5 and 1.0%) produces a decrease in nC8 conversion and in cracking products. The metallic properties of Pt are decreased by its strong interaction with the support, mainly with sulfate zirconia; at the same time, Pt decreases the acid cracking activity of the support.Fil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Yori, Juan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Parera, Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Pt-Co and Pt-Ni Catalysts of Low Metal Content for H2 Production by Reforming of Oxygenated Hydrocarbons and Comparison with Reported Pt-Based Catalysts

New catalysts of Pt, PtNi, PtCo, and NiCo supported on Al2O3 were developed for producing hydrogen by aqueous phase reforming (APR) of oxygenated hydrocarbons. The urea matrix combustion technique was used for loading the metal on the support in order to improve several aspects: increase both the metal-support interaction and the metal dispersion and decrease the metal load. The catalysts were characterized by MS/ICP, N2 adsorption, XRD, TPR, CO chemisorption, and the test of cyclohexane dehydrogenation (CHD). The APR of a solution of 10% mass ethylene glycol (EG), performed in a tubular fixed bed reactor at 498 K, 22 bar, WHSV = 2.3 h-1, was used as the main reaction test. After 10 h on-stream, the catalysts prepared by UMC had better hydrogen yield and catalytic stability than common catalysts prepared by IWI. The UMC/IWI H2 yield ratio was 23.5/15.2 for Pt, 24.0/17.0 for PtCo, 26.6/21.0 for PtNi, and 8.0/3.9 for NiCo. Ni or Co addition to Pt increased the carbon conversion while keeping the H2 turnover high. Cobalt also improves stability. Reports of several authors were revised for a comparison. The analysis indicated that the developed catalysts are a viable and cheaper alternative for H2 production from a renewable resource.Fil: Dosso, Liza Ainalen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Promoting light hydrocarbons yield by catalytic hydrodechlorination of residual chloromethanes using palladium supported on zeolite catalysts

Gas catalytic hydrodechlorination (HDC) of trichloromethane (TCM) and dichloromethane (DCM) was analyzed using Pd (1 wt.%) on different zeolites as catalysts. The aim of this study was to know the surface properties of the catalysts and reaction conditions that promote the yield to light hydrocarbons in this reaction. Five different zeolite supports were used from three commercial zeolites (KL, L-type; NaY, Faujasite; H-MOR, Mordenite). KL and NaY were submitted to ionic exchange treatments in order to increase their acidity and analyze the effect of the acidity in the activity and selectivity of the HDC reaction. Exchanged zeolites (HL and HY) showed the highest Pd dispersion due to their higher surface acidity. The best TCM/DCM conversion and selectivity to light hydrocarbons was obtained using the two non-exchanged zeolite-catalysts, KL and NaY. Low surface acidity seems to be the key aspect to promote the formation of light hydrocarbons. The formation of these products is favored at high reaction temperatures and low H2: chloromethane ratios. KL showed the highest selectivity to olefins (60%), although with a lower dechlorination degree. Non-exchanged NaY catalyst showed high selectivity to paraffins (70% and 95% for the HDC of DCM and TCM, respectively)Authors gratefully acknowledge financial support from FEDER/Ministerio de Ciencia, Innovación y Universidades—Agencia Estatal de Investigación/ CTM2017-85498-R. C. Fernández Ruiz acknowledges MINECO for his research gran

Characterization and Behaviour of Pt Catalysts Supported on Basic Materials in Dry Reforming of Methane

Different basic materials, such as K-L zeolite, K-Al2O3, K-Mg/Al mixed oxide and MgO, were used as supports of Pt-catalysts for the dry reforming of methane (DR) reaction. The effects of the distribution of basic strength in the support on the metal-support properties and catalyst performance were evaluated. The density of strong and the total basic sites decreased as follows: MgO>K(Mg-Al) >K-Al2O3 >K-L. The total basic sites decrease from 214 to 23 µmol CO2.g-1, for MgO and KL, respectively. Pt catalysts supported on materials with high density of strong basic sites such as MgO were the most adequate for the DR reaction. An increase in the dehydrogenation velocity of 12.1 to 25.2 mol h-1 g-1 was observed between Pt/KL and Pt/MgO, which indicates a higher metallic dispersion of the latter catalyst. With respect to the DR reaction, both catalysts have a similar CO2 conversion, but the CH4 conversion and the H2 /CO ratio increase from 71.1 to 83.0 % and 0.5 to 0.73, respectively. The best catalytic behaviour of Pt/MgO would be related with the good interaction between the metal and the basic support. The methane conversion and the H2/CO ratios obtained by DR reaction correlate quite well with the basicity of the different catalysts.Fil: Ballarini, Adriana Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: C.F. Virgens. Universidade Do Estado Da Bahiadepartamento de Ciência; BrasilFil: Rangel, Maria do Carmo. Universidade Federal da Bahia; BrasilFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Grau, Javier Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Highly dispersed Fe3+-Al2O3 for the Fenton-like oxidation of phenol in a continuous up-flow fixed bed reactor: enhancing catalyst stability through operating conditions

A highly dispersed Fe3+-Al2O3 catalyst (6 wt% Fe) was used for the catalytic wet hydrogen peroxide oxidation of phenol (1 g/L) in an up-flow fixed bed reactor (UFBR) under continuous operation. To enhance catalytic performance, three simple synthesis strategies were combined: two-stage impregnation of iron citrate, acid washing with CH3COOH and thermal treatment at 900 °C. Solid samples were characterized in depth by several techniques: N2 Physisorption, XRD, SEM–EDAX, TEM, TGA, PZC, TPD of pyridine, XPS and Mössbauer. Peroxidation experiments were performed in an UFBR over a wide range of operating parameters in order to evaluate their influence on phenol mineralization and catalyst stability. Under selected operating condition (T = 90 °C, Wcat = 20 g, QL = 1.2 mL/min and [H2O2]:[Phenol] = 16.8), complete phenol conversion and remarkable TOC reduction of 90% were achieved, with a high H2O2 consumption efficiency (η = 76%) and low Fe leaching ( 70%) but the cumulative iron loss was calculated to be c.a. 20% of the initial Fe loaded in the UFBR. The catalyst was susceptible to leaching due to the accumulation of complexing intermediates such as carboxylic acids. However, acceptable iron leaching values ( 80%). The presence of chelating by-products favored also the Fe redistribution inside the catalyst pellets. Nevertheless, catalyst decay in the long-term operation was mainly due to the occurrence and permanence of chelating organic acids. This process was specially promoted by the amphoteric character of the alumina-based catalyst. However, adsorbed species were promptly eliminated by calcination at 500 °C, recovering steady state conversion profiles.Centro de Investigación y Desarrollo en Ciencias Aplicada