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1.
The catalytic conversion of CO2 is an important component for the reintegration of secondary products like CO2 or H2 into the energy supply. An example is the “power to gas” concept with a conversion of CO2 into CH4. The CO2 is transferred into a carrier of chemical energy, with the possibility to feed the produced CH4 into the existing network of natural gas. At temperatures of around 350 °C, hydrogenation of CO2 to CH4 is possible by the Sabatier reaction CO2 + 4H2 → CH4 + 2H2O. One prerequisite for efficient kinetics of the Sabatier reaction is the application and optimization of catalysts. The focus of catalyst development is given to their performance under the conditions to be expected in the special application. As a part of the project Geoenergy-Research (GeoEn), we address questions related to the catalytic utilization of CO2 produced in the course of the oxyfuel combustion of lignite. In this contribution, we report on the experimental setup in laboratory scale, which enables an advanced characterization of the catalytic performance, including thermodesorption measurements at atmospheric pressure in order to determine the amount of adsorbed CO2 under real conditions. We also show data for activation energies, the catalytic performance as function of temperature and the long time stability of a commercial Ru-based catalyst.  相似文献   

2.
Dimethyl phthalate (DMP) is ubiquitous in aquatic environments due to extensively used as plasticizer, which has received increasing attention in recent years. In this study, the catalytic ozonation of dimethyl phthalate was performed using Ce-substituted goethite as a novel catalyst, which was prepared by isomorphous substitution method. The specific surface area, pHpzc and surface hydroxyl density of the catalyst were determined. The catalyst was characterized using X-ray diffraction, scanning electron microscope and Fourier transform infrared spectroscopy. The removal efficiency of DMP was almost 100% after 30 min, and about 40% DMP was mineralized after 60 min, which was nearly four times higher than single ozonation. During catalytic ozonation process, anions (PO4 3?, SO4 2?, Cl?) affected DMP degradation, indicating that surface hydroxyl groups on the surface of catalyst were main active sites. The electron transfer process by redox reaction between Ce3+/Ce4+, Fe2+/Fe3+ was proposed, and their interaction could also promote the formation of hydroxyl radicals. Ce-substituted goethite was an efficient catalyst for degradation of DMP by catalytic ozonation.  相似文献   

3.
Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C5, 2% C1) to predominantly light hydrocarbons (56% C1, 8% C5), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results.  相似文献   

4.
Aluminum-containing hexagonally ordered mesoporous silica (Al-MCM-41) with specific surface area of 509.4 m2/g was first synthesized using natural halloysite as source material by hydrothermal treatment, without addition of silica or aluminum regents. The samples were characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption–desorption measurements, and Fourier transform infrared spectra techniques. The results indicate that process parameters, including calcination temperature, pH value, n(SiO2)/n(CTAB)/n(H2O) ratio, and hydrothermal reaction time, show moderate effects on the preparation of Al-MCM-41. SiO2/Al2O3 molar ratio could be effectively modulated by the calcination temperature for halloysite. Furthermore, we first clarified the structural evolution from natural halloysite to mesoporous material Al-MCM-41 at the atomic level.  相似文献   

5.
The kinetics of spent nickel oxide catalyst (NiO/Al2O3) leaching in sulphuric acid solutions was investigated. The effects of sulphuric acid concentration, temperature, stirring speed, and particle size on the rate of nickel leaching were studied. In addition, the reaction residues at various levels of nickel extraction were examined by SEM, X-ray diffraction, electron microprobe, and chemical analysis. The results of the kinetic analysis of the leaching data for various experimental conditions indicated that the reaction is controlled by diffusion through the catalyst network with the activation energy of 16.6 ± 0.9 kJ/mol. A linear relationship between the rate constant and the inverse square of the initial particle diameter is also characteristic for a diffusion-controlled process.  相似文献   

6.
Spent hydro-refining catalysts mainly consists of 20–22% MoO3, 5–6% NiO, 4–5% S, 1–2% Co3O4, 1.3–1.5% Fe2O3, 3–4% SiO2, and the balance is Al2O3. In the present study, one such spent catalyst was roasted with sodium chloride to recover molybdenum by converting it into sodium molybdate. The sodium molybdate was further purified by chemical treatment to obtain a pure grade molybdenum trioxide. Various parameters like temperature, time and NaCl addition have been studied, and conditions for the maximum recovery of molybdenum have been established.  相似文献   

7.
We have measured activity coefficients for NiO and FeO in a variety of silicate melts (SiO2-CaO-MgO-Al2O3) using electrochemical methods similar to square wave voltametry. We report the activity of the oxide ion (aO2−) in one composition. Based on these measurements, we have constructed a model that predicts the variations in activity we observe, and also variations in NiO activity reported in the literature. Activity of metal-oxide components such as NiO and FeO in silicate melts can be understood by considering contributions from both the activity of the oxide ion and the activity of the cation through expressions of the type:
  相似文献   

8.
Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50–60 vol % of X-ray amorphous components. X-ray amorphous nanosized Mn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe2O3, 7.11 SiO2, 2.41 CaO, 17.90 TiO2, 1.74 Na2O, 1.73 Al2O3, 1.30 MgO, 1.25 P2O5, 1.25 SO3, 0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K2O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodulesis as follows (wt %): 48.35 MnO, 6.23 Fe2O3, 8.76 MgO, 5.05 Al2O3, 4.45 SiO2, 3.63 NiO, 2.30 Na2O, 2.19 CuO, 1.31 CaO, and 0.68 K2O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10–20 μm in size were identified in ferromanganese nodules as well. The formation of nativemetals can be explained by their crystallization at highly reducing conditions maintained by organic matter.  相似文献   

9.
Experimental study of the effect of SiO2 on Ni solubility in silicate melts   总被引：1，自引：0，他引：1  
A. A. Borisov 《Petrology》2006,14(6):530-539
The solubility of Ni in silicate melts with variable SiO2 content was studied at a total pressure of 1 atm within a wide range of temperature and oxygen fugacity. The maximum solubility of Ni (minimum activity coefficient of NiO) was observed in melts with ～55–57 wt % SiO2, regardless of temperature and oxygen fugacity. Melts beyond this range showed significantly lower Ni solubility and, correspondingly, higher NiO activity coefficients. The analysis of our results and literature data led us to the conclusion that the NBO/T (number of nonbridging oxygen atoms per tetrahedrally coordinated atom) is inadequate to describe the effect of melt composition on Ni solubility.  相似文献   

10.
传统的Fenton均相亚铁盐催化剂处理染料废水,具有难以避免的二次污染和亚铁离子流失问题。分子筛催化剂相比传统催化剂具有高效环保的特点,在催化氧化染料废水领域有着良好的前景。本文通过液相离子交换法制备了Fe-ZSM-5非均相分子筛催化剂,替代传统的亚铁盐催化剂,应用X射线衍射对制备的Fe-ZSM-5分子筛催化剂进行表征,表明随离子交换次数的增加,Fe-ZSM-5催化剂负载的铁量上升,且较好地保持了分子筛结构,有利于提高亚铁离子的催化能力。通过实验确定了Fe-ZSM-5催化剂催化反应的最佳温度、pH值、Fe-ZSM-5的用量、反应时间等工艺参数,比较了Fe-ZSM-5催化剂和传统Fenton均相催化剂降解染料废水的脱色率和废水中铁离子的残留量,结果表明Fe-ZSM-5的脱色率达到98.5%,相比于Fenton均相催化剂的脱色率提升约3%;两种催化剂的铁离子残留量差别显著,Fe-ZSM-5催化剂处理的废水中只产生微量的Fe离子,可以认为Fe-ZSM-5非均相分子筛催化剂有效地解决了催化剂损耗和二次污染问题。  相似文献   

11.
The extensive use of Rhodamine B (RhB) for textile, paper, pigment, food, cosmetic, and drug manufacturing and its indiscriminate disposal leads to serious human, biological, and environmental hazards. A magnetic adsorbent with silicate and phenyl polymers (Ph/SiO2/Fe3O4) has been prepared to absorb RhB. The morphology and structure of the adsorbents have been characterized by TGA, XRD, FTIR, and adsorption–desorption measurement. The results revealed that Ph/SiO2/Fe3O4 exhibited a paramagnetic behavior and could easily and quickly be separated from a suspension. The RhB adsorption behavior was almost pH independent due to the adsorption between the phenyl ring of Ph/SiO2/Fe3O4 and RhB by π–π electron-donor–acceptor interactions. The adsorption behavior of RhB adsorption was in good agreement with the Langmuir adsorption isotherm, and the maximum adsorption capacity was 142.186 mg g?1. Good desorption performance of Ph/SiO2/Fe3O4 showed that this novel magnetic adsorbent cannot only be activated by ethanol extraction process but also reuse by the recovery of magnetic force.  相似文献   

12.
This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.  相似文献   

13.
Insight into the complexation of organic molecules on hematite surfaces was obtained from molecular-level studies of a simple probe molecule (methanol) with the R-cut surface of hematite. The R-cut crystal orientation of hematite, designated in this paper as α-Fe2O3(012), has two stable surface structures under ultrahigh vacuum (UHV) conditions based on low-energy electron diffraction (LEED) measurements. These are a (1×1) structure consisting of a bulk terminated arrangement of undercoordinated Fe3+ and O2− surface sites and a (2×1) reconstructed structure with unknown atomic structure. Whereas the (1×1) surface is essentially free of Fe2+, the (2×1) surface possesses a high surface concentration of Fe2+ sites based on electronic structure measurements using electron energy loss spectroscopy (EELS). Methanol adsorbs dissociatively on the (1×1) surface by coordination of the molecule’s oxygen atom at a Fe3+ site followed by transfer of the alcohol proton to a bridging O2− surface site, resulting in terminal OCH3 and bridging OH groups. Most of the dissociated methanol molecules recombine during heating and desorb in vacuum as methanol at 365 and 415 K for the (1×1) and (2×1) surfaces, respectively. However, a significant amount of the terminal OCH3 and bridging OH groups interchange as the surface is heated above room temperature (RT), resulting in bridging OCH3 and terminal OH groups. The bridging OCH3 groups are retained on the surface to higher temperature than the terminal OCH3 groups, but eventually decompose at about 550 K via a disproportionation reaction that forms gaseous CH3OH and H2CO. As a result of the disproportionation reaction, some surface Fe3+ sites are reduced to Fe2+ sites. The exchange process competes more successfully with recombinative desorption of methanol (from reaction of terminal OCH3 and bridging OH groups) on the (2×1) surface, despite the fact that this surface is already partially reduced, because terminal OCH3 groups are more stable on this surface than on the (1×1) surface. Based on these molecular-level findings, extensive exchange terminal organic ligands and bridging OH groups may play a significant role in stabilizing organics on hematite mineral surfaces. Such exchange processes may also play a role in destabilizing hematite surfaces toward reductive dissolution.  相似文献   

14.
The reaction chloritoid (ctd)=almandine (alm)+diaspore+H2O (CAD) has been reversed using Fe3+-free synthetic chloritoid and almandine, under fO2 conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO2 conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO2 conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH2O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H2O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H2O bracketed on the Fe/FeO buffer and under unbuffered fO2 conditions. For fO2 buffered by the assemblage Fe/FeO, aH2O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO2 buffered by the assemblage Ni/NiO, aH2O=1. The aH2O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H2O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H o f,ctd and S octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and KD=(Fe3+/Al)ctd/(Fe3+/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe3+ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl2SiO5(OH)2 formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe3+ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H2O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for KD=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the KD values reported from chloritoid+garnet+quartz+kyanite natural assemblages.  相似文献   

15.
The Claus process has been used for the conversion of H2S and SO2 to elemental sulfur. These two sulfur compounds need special attention because they are very poisonous with negative impact on both the environment and human health. Here, highly active Fe–Ni/TiO2 catalyst has been prepared and shaped by three different binders (bentonite, polyethylene glycol and carboxymethyl cellulose) into extrudes. Comparing the mechanical strength and surface area of prepared extrudes, the optimal shaped catalyst was selected with 20% of bentonite, 2% of PEG and 2% of CMC. The optimal catalyst was characterized by X-ray powder diffraction, temperature-programmed reduction, Brunauer–Emmett–Teller specific surface area, Barrett–Joyner–Halenda, scanning electron microscopy and energy-dispersive X-ray techniques and used for sulfur recovery process. The performance of this product for sulfur recovery via Claus process was excellent with the conversion of hydrogen sulfide of 76.77% and sulfur dioxide of 97.83%. The catalyst also provides high hydrolysis activity of CS2 (83.06%). Therefore, a highly active TiO2-supported shaped catalyst with 85.62% of conversion efficiency has been prepared successfully to convert the small amounts of H2S, SO2 and CS2 to elemental sulfur.  相似文献   

16.
Multi-walled carbon nanotubes (MWCNTs) embedded in SiO2 particles were prepared through the floating-catalyst chemical vapor deposition method. The parameters reaction time and flow rate of the carbon source (CH4) were studied to obtain optimum conditions for MWCNT synthesis. The obtained MWCNTs were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy to confirm their morphology and crystallinity. The optimum conditions were a CH4 flow rate of 100 ml/min in a H2–Ar mixture at a flow rate of 500 ml/min and a reaction time of 20 min. Under these conditions, MWCNTs with average outer and inner diameters of around 50 and 10 nm, respectively, were obtained. SiO2 particles with embedded MWCNTs were studied for their adsorption of gaseous chlorinated phenolic compounds (CPCs), with emphasis on the effect of number of chlorine substituents. The CPC compounds of 2-chlorophenol (CP) and 2,4-dichlorophenol (DCP) were compared against phenol (P). Adsorption of P and CPCs on the particles fit well the Langmuir isotherm. The adsorption capacities of P, CP, and DCP on SiO2 particles with embedded MWCNTs were found to be 3.12, 13.83, and 44.25 mg/g, respectively. Desorption activation energy was determined by thermogravimetric analysis. Chlorine substitution on P changed the adsorption process from physical to chemical adsorption. The particles showed high potential for use as a pre-concentration unit for solid-phase microextraction.  相似文献   

17.
The equation of state and pressure-induced structural evolution of pyrite-type SiO2 have been investigated based on synchrotron X-ray diffraction measurements in a diamond-anvil cell. The Rietveld refinement revealed that the oxygen coordinate x of pyrite-type SiO2 increases with increasing pressure. The SiO6 coordination polyhedra of pyrite-type SiO2 is less compressible than the unit cell, and the increase in x induces a rotation of the SiO6 coordination polyhedra to fill the blank space in the unit cell. Thus, the volume reduction in pyrite-type SiO2 is achieved mainly by the rotation of the SiO6 polyhedra, rather than by the compression of the SiO6 polyhedra. In addition, the increase in x with increasing pressure enhances a distortion of the coordination polyhedra of pyrite-type SiO2, implying that pyrite-type SiO2 is not likely to transform into a fluorite-type structure at higher pressures.  相似文献   

18.
Viscosity measurements are reported for amorphous silica and liquids belonging to the systems SiO2-M, SiO2-Al2O3-M, where M is an alkali-earth metal oxide, MnO, or alumina, and the systems SiO2-“FeO”, SiO2-FeO-Fe2O3-CaO, and SiO2-Al2O3-N, where N = Na2O or K2O. The implications of these measurements concerning the coordination of Al and the structure of these liquids are briefly discussed. Stable liquids in the systems SiO2-Al2O2-M show a non-Arrhenian temperature dependence of their viscosity, in general. Results obtained with empirical methods to calculate the viscosity of silicate liquids are compared with our observations.  相似文献   

19.
The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H2O and O2 on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O2 was controlled at the Fe0–FeO, FeO–Fe3O4, or Ni0–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO2, and the fugacities of H2O and O2. Of these variables, the fugacity of H2O has the strongest influence. The solubility of H in olivine increases with increasing SiO2 activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm?1. The heights of peaks at 3,330 and 3,356 cm?1 correlate positively with O2 fugacity, while those at 3,525 and 3,572 cm?1 correlate with H2O fugacity.  相似文献   

20.
Fixation of Mo in sulfidic environments is believed to be preceded by conversion of geochemically passive MoO42− to particle-reactive thiomolybdates (MoOxS4−x2−). In aqueous solution, these transformations are general-acid catalyzed, implying that proton donors can accelerate both the forward and reverse reactions. Here, we explore whether mineral surfaces also catalyze thiomolybdate interconversions. The rate of MoS42− hydrolysis is investigated in the presence and absence of natural kaolinite (KGa-1b) and synthetic Al2O3 and SiO2 phases. Comparison of rates achieved with these phases suggests that the Al oxyhydroxide component in kaolinite furnishes the catalytic activity. An anhydrous Al2O3 phase is catalytically inactive until hydrated (and therefore protonated). Surface kinetics with kaolinite at mildly alkaline pH are consistent with rate limitation by formation or decomposition of monomeric surface complexes; oligomeric surface intermediates may become important at MoS42− > 20 μmol/L, higher than is likely to be found in nature. The pH dependence of the kaolinite-catalyzed reaction suggests that weak-acid surface sites promote hydrolysis. Intermediate thiomolybdates or molybdate appears to compete for active sites, inhibiting MoS42− hydrolysis. Catalysis of MoOS32− hydrolysis is also observed but has not been studied systematically. Thiomolybdate hydrolysis is inhibited slightly by sulfate and more strongly by phosphate. Low NaCl concentrations (<10−2 mol/L) promote hydrolysis, but higher NaCl concentrations retard the reaction to a small extent. A mechanism is postulated involving expansion of the coordination number around Mo from 4 to 6 under the influence of the surface. The effective concentration of surface sites available to Mo in sediment pore waters is likely to be large enough to greatly accelerate thiomolybdate hydrolysis and sulfidation. Possibly this explains why Mo capture in seasonally or intermittently anoxic environments often occurs through processes operating within sediments but not in overlying waters.  相似文献   

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