Investigation on the Suitability of Engelhard Titanium Silicate as a Support for Ni-Catalysts in the Methanation Reaction

Methanation reaction of carbon dioxide is currently envisaged as a facile solution for the storage and transportation of low-grade energies, contributing at the same time to the mitigation of CO2 emissions. In this work, a nickel catalyst impregnated onto a new support, Engelhard Titanium Silicates (ETS), is proposed, and its catalytic performance was tested toward the CO2 methanation reaction. Two types of ETS material were investigated, ETS-4 and ETS-10, that differ from each other in the titanium content, with Si/Ti around 2 and 3% by weight, respectively. Catalysts, loaded with 5% of nickel, were tested in the CO2 methanation reaction in the temperature range of 300–500 °C and were characterized by XRD, SEM–EDX, N2 adsorption–desorption and H2-TPR. Results showed an interesting catalytic activity of the Ni/ETS catalysts. Particularly, the best catalytic performances are showed by Ni/ETS-10: 68% CO2 conversion and 98% CH4 selectivity at T = 400 °C. The comparison of catalytic performance of Ni/ETS-10 with those obtained by other Ni-zeolites catalysts confirms that Ni/ETS-10 catalyst is a promising one for the CO2 methanation reaction.

From structure topology to chemical composition. XXVIII. Titanium silicates: Jinshajiangite from the Oktyabr'skii Massif, Donetsk Region, Ukraine, a new occurrence

ABSTRACT Here we report electron-microprobe data and unit-cell parameters for jinshajiangite, ideally NaBaFe2+4Ti2(Si2O7)2O2(OH)2F, from a new locality: the Oktyabr'skii massif in the coastal area of the Azov Sea, Donetsk region, Ukraine. Chemical analysis by electron microprobe gave Nb2O5 1.59, ZrO2 0.61, TiO2 17.07, SiO2 27.60, Al2O3 0.08, Fe2O3 2.04, FeO 16.42, BaO 9.81, ZnO 0.76, MnO 12.97, CaO 1.82, MgO 0.07, K2O 2.05, Na2O 2.51, F 2.48, H2O 1.92, O = F –1.04, sum 98.76 wt.%; H2O was determined in accord with the required number of monovalent anions for the Ti-dominant perraultite-type minerals: OH + F = 3 pfu; the Fe3+/Fe2+ ratio was assigned in accord with Mössbauer-spectroscopy results for jinshajiangite from a different locality. The empirical formula calculated on the basis of 19 (O + F) is (Na0.71Ca0.28□0.01)Σ1(Ba0.56K0.38□0.06)Σ1(Fe2+1.99Mn1.59Fe3+0.22Zn0.08Mg0.02Al0.01□0.09)Σ4 (Ti1.86Nb0.10Zr0.04)Σ2(Si4.00O14)O2[(OH)1.86F0.14]Σ2F1.00, Z = 4. Unit-cell parameters from the single-crystal data were determined by least-squares refinement of 9807 reflections with I > 10σI and are as follows: a = 10.726(8), b = 13.834(10), c = 11.065(8) Å, α = 108.172(5), β = 99.251(7), γ = 90.00(1)°, V = 1537.5(3.4) Å3, space group C .

Titanium Silicates Precipitated on the Rice Husk Biochar as Adsorbents for the Extraction of Cesium and Strontium Radioisotope Ions

The aim of the work was the development of cheap and effective adsorbents based on titanium silicates deposited on the products of thermochemical processing of rice husk to extract cesium and strontium radioisotopes from aqueous media. Synthesis of adsorbents was carried out using the cheapest and widely used titanium water-soluble reagent, titanium sulfate (an intermediate product of white rutile pigment production), as feedstock. After treatment with titanium sulfate and neutralization, hydrothermal treatment was carried out in various ways. The traditional method of processing in an autoclave was used, as well as the blowing at different temperatures by steam. The distribution coefficients and the adsorption capacity for cesium and strontium ions on these sorbents were studied. Along with the chemical composition of adsorbents obtained by those ways, the type and the temperature of hydrothermal treatment also affected the adsorption properties. It was found that the adsorbent obtained by hydrothermal treatment in an autoclave has the highest degree of cesium ions extraction (Kd = 27,500). The highest degree of strontium ions extraction (Kd = 2,095,000) has an adsorbent obtained by hydrothermal treatment with water vapor blowing.

From structure topology to chemical composition. XX. Titanium silicates: the crystal structure of hejtmanite, Ba2Mn4Ti2(Si2O7)2O2(OH)2F2, a Group-II TS-block mineral

The crystal structure of hejtmanite, Ba2Mn4Ti2(Si2O7)2O2(OH)2F2, from Mbolve Hill, Mkushi River area, Central Province, Zambia (holotype material) has been refined on a twinned crystal toR1= 1.88% on the basis of 4539 [|F| > 4|F|] reflections. Hejtmanite is triclinic,C1̅,a= 10.716(2),b= 13.795(3),c= 11.778 (2) , = 90.07(3), = 112.24(3), = 90.03(3),V= 1612(2)3. Chemical analysis (electron microprobe) gives: Ta2O50.09, Nb2O51.27, ZrO20.65, TiO214.35, SiO223.13, BaO 26.68, SrO 0.19, FeO 11.28, MnO 15.12, Cs2O 0.05, K2O 0.33, F 3.82, H2Ocalc. 1.63, O = F 1.61, total 97.10 wt.%, where the H2O content was calculated from the crystal-structure refinement, with (OH F) = 4 apfu. The empirical formula, calculated on the basis of 20 (O F) anions, is of the form(Si2O7)2(XO)4(XP)2, Z=4: (Ba1.82K0.07Sr0.02)Σ1.91(Mn2.33Zr0.04Mg0.03)Σ3.95(Ti1.88Nb0.10Zr0.02)Σ2(Si2.02O7)2O2[(OH)1.89F0.11]Σ2F2. The crystal structure is a combination of a TS (Titanium Silicate) block and an I (intermediate) block. The TS block consists of HOH sheets (H heteropolyhedral, O octahedral). The topology of the TS block is as in Group-II TS-block minerals: Ti ( Nb) = 2 apfu per (Si2O7)2[as defined by Sokolova (2006)]. In the O sheet, five[6]MOsites are occupied mainly by Mn, less Fe2and minor Zr and Mg, with <MOφ> = 2.198 (φ = O,OH), ideally giving Mn4apfu. In the H sheet, two[6]MHsites are occupied mainly by Ti, with <MHφ> = 1.962 (φ = O,F), ideally giving Ti2apfu; four[4]Sisites are occupied by Si, with < SiO> = 1.625 . The MHoctahedra and Si2O7groups constitute the H sheet. The two[12]Ba-dominant AP(1,2) sites, with <APφ> = 2.984 (φ = O, F), ideally give Ba2apfu. Two(1,2) and two(1,2) sites are occupied by O atoms and OH groups with minor F, respectively, ideally giving (XO)4= ()2()2=O2(OH)2pfu. Two(1,2) sites are occupied by F, giving F2apfu. TS blocks link via a layer of Ba atoms which constitute the I block. Simplified and end-member formulae of hejtmanite are Ba2(Mn,Fe2)4Ti2(Si2O7)2O2(OH,F)2F2and Ba2Mn4Ti2(Si2O7)2O2(OH)2F2,Z= 4. Hejtmanite is a Mn-analogue of bafertisite, Ba24 Ti2(Si2O7)2O2(OH)2F2.