• Journal of Hydrogen and New Energy
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• v.18 no.2
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• pp.124-131
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• 2007

Methane is partially oxidized to produce the syngas by the lattice oxygen of metal oxides in the absence of gaseous oxygen. The present work deals with ferrite including copper component, which does not chemisorb methane, to investigate the suppression of the carbon deposition during the reduction of metal oxides by methane. Iron-based oxides of $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0) was synthesized by the co-precipitation method. Thermogravimetric Analysis(TGA) was used to observe the isothermal reduction behavior of $Cu_xFe_{3-x}O_4$ and $Fe_3O_4$ at $600-900^{\circ}C$ under methane atmosphere. The crystal structures of reduced specimens were characterized by X-rays powder diffraction(XRD) technique. From the analyses of TGA, it is concluded that the reduction kinetics of $CuFe_2O_4$ was the fastest among $Fe_3O_4$ and $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0). The X-ray diffraction analyses indicated that $Cu_xFe_{3-x}O_4$ was decomposed to Cu and $Fe_3O_4$ phase at $600^{\circ}C$ and was reduced to Cu and Fe phase at $800^{\circ}C$. $Fe_3O_4$, which was reduced at $900^{\circ}C$, showed Fe, graphite and $Fe_3C$ phases. On the contrary, $Cu_xFe_{3-x}O_4$ does not show the graphite or $Fe_3C$ phases. This results infer that Cu component suppress the carbon deposition on Cu-ferrite.

• Resources Recycling
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• v.26 no.3
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• pp.17-25
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• 2017

Electric arc furnace steelmaking dust has various physicochemical properties as volatile components generated in the melting process of steel scraps in an electric arc furnace, which is captured in oxide form as fine powder by reacting with oxygen in the air. In order to efficiently recycle these electric arc furnace dust, a kinetic basic experiment and a pilot production test were carried out in parallel. As a result, it was found that the electric arc furnace dust contain a large amount of Cl and alkali components, thus it was expected that the compounds have a great adverse effect on the actual operation for the recycling. It was confirmed that the volatilization behavior was progressing actively at $1100^{\circ}C$ and the electric arc furnace dust was melted at $1250^{\circ}C$. These results are the same as a result of pilot test for the formation behavior of zinc oxide and reduced iron. These results should be useful as basic data for designing the recycling plant of the electric arc furnace dust and establishing the operating conditions.

• Journal of the Mineralogical Society of Korea
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• v.21 no.3
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• pp.227-237
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• 2008

Arsenic has recently become of the most serious environmental concerns, and the worldwide regulation of arsenic fur drinking water has been reinforced. Arsenic contaminated groundwater and soil have been frequently revealed as well, and arsenic contamination and its treatment and measures have been domestically raised as one of the most important environmental issues. Arsenic behavior in geo-environment is principally affected by oxides and clay minerals, and particularly iron (oxy)hydroxides have been well known to be most effective in controlling arsenic. Among a number of iron (oxy)hydroxides, for this reason, 2-line ferrihydrite was selected in this study to investigate its effect on arsenic behavior. Adsorption of 2-line ferrihydrite was characterized and compared between As(III) and As(V) which are known to be the most ubiquitous species among arsenic forms in natural environment. Two-line ferrihydrite synthesized in the lab as the adsorbent of arsenic had $10\sim200$ nm for diameter, $247m^{2}/g$ for specific surface area, and 8.2 for pH of zero charge, and those representative properties of 2-line ferrihydrite appeared to be greatly suitable to be used as adsorbent of arsenic. The experimental results on equilibrium adsorption indicate that As(III) showed much stronger adsorption affinity onto 2-line ferrihydrite than As(V). In addition, the maximum adsorptions of As(III) and As(V) were observed at pH 7.0 and 2.0, respectively. In particular, the adsorption of As(III) did not show any difference between pH conditions, except for pH 12.2. On the contrary, the As(V) adsorption was remarkably decreased with increase in pH. The results obtained from the detailed experiments investigating pH effect on arsenic adsorption show that As(III) adsorption increased up to pH 8.0 and dramatically decreased above pH 9.2. In case of As(V), its adsorption steadily decreased with increase in pH. The reason the adsorption characteristics became totally different depending on arsenic species is attributed to the fact that chemical speciation of arsenic and surface charge of 2-line ferrihydrite are significantly affected by pH, and it is speculated that those composite phenomena cause the difference in adsorption between As(III) and As(V). From the view point of adsorption kinetics, adsorption of arsenic species onto 2-line ferrihydrite was investigated to be mostly completed within the duration of 2 hours. Among the kinetic models proposed so for, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto 2-line ferrihydrite.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.197-210
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• 2012

Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).

• KSCE Journal of Civil and Environmental Engineering Research
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• v.31 no.2B
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• pp.187-192
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• 2011

Nitrate nitrogen is common contaminant in groundwater aquifers, its concentration is regulated many countries below 10 mg/L as N (As per WHO standards) in drinking water. An attempt was made to get optimal results for the treatment of nitrate nitrogen in groundwater by conducting various experiments by changing the experimental conditions for ZVI bipolar packed bed electrolytic cell. From the experimental results it is evident that the nitrate nitrogen removal is more effective when the reactor conditions are maintained in acidic range but when the acidic environment changes to alkaline due to the hydroxide formed during the process of ammonia nitrogen there by increasing the pH reducing the hydrogen ions required for reduction which leads to low effectiveness of the system. In the ZVI bipolar packed bed electrolytic cell, the packing ratio of 0.5~1:1 was found to be most effective for the treatment of nitrate nitrogen because ZVI particles are isolated and individual particle act like small electrode with low packing ratio. It is seen that formation of precipitate and acceleration of clogging incrementally for packing ratio more than 2:1, decreasing the nitrate nitrogen removal rate. When the voltage is increased it is seen that kinetics and current also increases but at the same time more electric power is consumed. In this experiment, the optimum voltage was determined to be 50V. At that time, nitrate nitrogen was removed by 94.9%.

• Resources Recycling
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• v.15 no.5 s.73
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• pp.3-10
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• 2006

The solvent extraction for the separation of platinum group metals from the leach liquor of spent automotive catalysts has been studied. Tri-n-butyl phosphate (TBP), tri-n-octylamine (TOA) and di-n-hexyl sulfide (DHS) were used as extractants and kerosene as a diluent. The extraction behavior of platinum, palladium and rhodium has been investigated as functions of different kinds of extractants and their concentrations. In addition, the extraction behavior of the major metal impurities such as cerium, lead, iron, magnesium and aluminum has been investigated. Platinum and palladium were extracted with TBP. And platinum, palladium and rhodium were extracted with TOA. Platinum was co-extracted with palladium into the organic phase by solvent extraction using SFI-6 of DHS extractant, but only palladium was selectively extracted with SFI-6R. The selective extraction of palladium with SFI-6R was found better than that with SFI-6, but the kinetics of extraction with SFI-6R was found poor in comparison to SFI-6. The metal impurities extracted simultaneously during the extraction of platinum group metals should be removed in scrubbing and stripping processes. A suitable process has been proposed for the separation of platinum group metals from the leach liquor of spent automotive catalysts. Initially palladium was extracted with SFI-6R, followed by the separation of platinum with TBP or TOA leaving rhodium in the raffinate.

• Korean Chemical Engineering Research
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• v.46 no.6
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• pp.1113-1118
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• 2008

Characteristics of reduction properties and carbon deposition of $CuFe_2O_4$ and $Fe_3O_4$ were investigated by using TGA, XRD, SEM, TEM and gas analysis at $900^{\circ}C$. XRD analyses indicated that the reduced $Fe_3O_4$ was composed of Fe, graphite and $Fe_3C$ phases. In contrast, the reduced $CuFe_2O_4$ did not show the graphite or $Fe_3C$ phases. It was observed by SEM analysis that the surface of the $Fe_3O_4$ was completely covered with carbon, after methane partial oxidation. From gas analysis, $CuFe_2O_4$ showed much higher methane conversion and reduction kinetics as compared to the $Fe_3O_4$ under the same reaction conditions and the estimated carbon deposition amounts on the reduced $CuFe_2O_4$ was much lower than those on the reduced $Fe_3O_4$ during the syngas production process. It was found by TEM that carbon on the reduced $Fe_3O_4$ particles has a platelet shape.

• Korean Journal of Soil Science and Fertilizer
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• v.44 no.6
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• pp.1063-1070
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• 2011

In this study, total of 5 different chemical amendments were evaluated for determining kinetic parameters and stabilization efficiency of heavy metals in aqueous phase. Standard solution of Cd and Pb ($100mg\;L^{-1}$) was mixed with various ratio of amendments (1, 3, 5, 10%) and heavy metal stabilization efficiency was monitored for 24hrs. All examined amendments showed over 90% of removal efficiency for both Cd and Pb except zerovalent iron (ZVI) for Cd (43-63%). Based on result of heavy metal stabilization efficiency, it was ordered as $CaCO_3$ > Dolomite > Zeolite > Steel slag > ZVI for both Cd and Pb in aqueous phase. For kinetic study, first order kinetic model was adapted to calculate kinetic parameters. In terms of reaction rate constants (k), zeolite showed the fastest reaction rate (k value from 0.4882 for 1% to 2.0105 for 10%) for Cd and ZVI (k value from 0.2304 for 1% to 0.5575 for 10%) for Pb. Considering reaction rate constant and half life for heavy metal stabilization, it was ordered as Zeolite > $CaCO_3$ > Dolomite > Steel slag > ZVI for Cd and $CaCO_3$ > Dolomite > Steel slag > Zeolite > ZVI for Pb. Overall result in this study can be interpreted that lime containing materials are more beneficial to remove heavy metals with high efficiency and less time consuming than absorbent materials.

• Economic and Environmental Geology
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• v.36 no.1
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• pp.39-48
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• 2003

The removal of chromate from aqueous solution using finely ground pyrite and biotite was investigated by batch experiments and the kinetics and the mechanism of chromate reduction were discussed. The chromate reduction by pyrite was about hundred times faster than that by biotite and was also faster at pH 3 than at pH 4. When pyrite was used, more than 90% of initial chromate was reduced within four hours at pH 4 and within 40 min. at pH 3. However, more than 400 hours was taken for the reduction of 90% of initial chromate by biotite. The results indicate that the rate of chromate reduction was strongly depending on the amount of Fe(II) in the minerals and on the dissolution rate of Fe(II) from the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH))$_3$$_{ (s)}$, which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than expected values. When biotite was used, amounts of decreased Fe(II) and reduced Cr(Ⅵ) did not show stoichiometric relationship, which implying there was not only chromate reduction by ferrous ions in the acidic solution but also heterogeneous reduction of ferric ions by the structural ferrous iron in biotite. However, the results from a series of the experiments using Pyrite showed that concentrations of the decreased Fe(II) and the reduced Cr(Ⅵ) were close to the stoichiometric ratio of 3:1. It was because the oxidation of pyrite rapidly created ferrous ions even in oxygenated solutions and the chromate reduction by the ferrous ions was significantly faster than ferrous ion oxygenation.

• Journal of the Korean Society of Groundwater Environment
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• v.7 no.3
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• pp.103-115
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• 2000

The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.