• Journal of the Korean Applied Science and Technology
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• v.35 no.3
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• pp.876-885
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• 2018

Utilization of spent RHDM(Residue Hydrodemetallation) catalyst as de-NOx SCR(Selective Catalytic Reduction) catalyst was studied by conducting by heptane cleaning and high-temperature roasting for removal of deposited carbon and sulfur. Followed by oxalic acid leaching was carried out for controlling excess vanadium deposited on spent RHDM catalyst in search of appropriate vanadium loadings for the best SCR performance and the leaching conditions are 5~15wt% concentration of oxalic acid and 5min leaching time at $50^{\circ}C$ with the ultra-sonic agitator. De-NOx activities of prepared and commercial SCR catalyst were measured by the atmospheric SCR catalyst performance test unit, their residual content were also carried out by ICP, C&S Analysis and XRF. Acid leaching (AL-10) catalyst showed the highest de-NOx efficiency of all prepared catalysts and the de-NOx efficiency over wash coated catalyst(WC-AL-10) was equivalent to that of commercial SCR catalyst. Therefore the possibility of using as SCR catalyst for each application by adjusting treatment conditions of spent RHDM catalyst was found and further research will be needed in detail for the its commercialization.

• Journal of the Korean Applied Science and Technology
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• v.37 no.4
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• pp.723-732
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• 2020

The spent RHDS (Residue HydroDeSulfurization) catalyst is deactivated mainly by deposition of various contaminants such as coke, sulfur and vanadium on the surface of catalyst. To eliminate those contaminants, the following remanufacturing process was conducted. The first, heavy oil on the surface of the spent RHDS catalyst was removed by kerosene and dehydrated. The second, the high temperature incineration was carried out to eliminate coke and sulfur components deposited on the surface of spent RHDS catalyst. The third, the excessive quantity of Vanadium deposited on the surface of catalyst was removed by leaching process as follows: ultrasonic agitation was carried out at 50℃, for 10 seconds with 0.5% and 1% oxalic acid solution. The purpose of this process is to find out regenerated RHDS catalyst can be used as SCR catalyst for NOx reduction by controlling the vanadium residual content of the regenerated RHDS catalyst through leaching process. The composition of regenerated RHDS catalyst was analyzed by XRF and the NOx reduction efficiency was also measured by continuous catalytic fixed bed reactor. As the result, regenerated catalyst, with 0.5% oxalic acid, ultrasonic agitation in 10 seconds, showed the most stable NOx reduction efficiency. Also, in comparison with commercial SCR catalyst, the NOx reduction performance of regenerated catalyst was similar to that of commercial SCR catalyst at the temperature 375℃ and higher whereas was lower than commercial SCR catalyst at the temperature range between 200~250℃. Therefore, it was confirmed that the regenerated catalyst as powder form wash coated on the surface of metal corrugated substrate can be used for commercial SCR catalyst.

• Resources Recycling
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• v.21 no.6
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• pp.65-73
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• 2012

Selective catalytic reduction(SCR) catalysts are obtained from de-NOx system of thermoelectric power plant. A process was developed for valuable metals such as vanadium and tungsten recovery from spent SCR catalyst by using soda roasting followed by water leaching. Spent SCR catalyst having $V_2O_5$(1.23 mass %) and $WO_3$(7.73 mass %). For getting soluble metal forms of the targeted metals like vanadium and tungsten soda roasting process was implemented. In soda roasting process, sodium carbonate added 5 equivalent ratio at roasted temperature $850^{\circ}C$ with 120 min roasted time for $544{\mu}m$ particle size of spent SCR catalyst. After soda roasting process moved to water leaching for roasted spent catalyst. Before leaching process the roasted spent catalyst was grinded up to $-45{\mu}m$ size. The leaching time is 30 min at $40^{\circ}C$ temperature, 10 % pulp density. The final leaching efficiency obtained 46 % of vanadium and 92 % of tungsten from present process.

• Resources Recycling
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• v.29 no.2
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• pp.62-68
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• 2020

In new millennium, wide-reaching demands for selective catalytic reduction (SCR) catalyst have been increased gradually in new millennium. SCR catalyst can prevent the NO_x emission to protect the environment. In SCR catalyst the main composition of the catalyst is typically TiO₂ (70~80%), WO₃ (7~10%), V₂O₅ (~1%) and others. When the SCR catalysts are used up and disposed to landfills, it is problematic that those should exist in the landfill site permanently due to their extremely low degradability. A new advanced technology needs to be developed primarily to protect environment and then recover the valuable metals. Hydrometallurgical techniques such as leaching and liquid-liquid extraction was designed and developed for the spent SCR catalyst processing. In a first stage, V and W selectively leached from spent SCR catalyst, then both the metals were processed by liquid-liquid extraction process. Various commercial extractants such as D2EHPA, PC 88A, TBP, Cyanex 272, Aliquat 336 were tested for selective extraction of title metals. Scrubbing and stripping studies were tested and optimized for vanadium and tungsten extraction and possible separation. 3^rd phase studies were optimized by using iso-decanol reagent.

• Korean Journal of Metals and Materials
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• v.46 no.12
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• pp.823-829
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• 2008

The solvent extraction process for the recovery of vanadium from leaching solution of SCR(selective catalytic reduction) spent catalyst was investigated by using Alamine336 as an extractant. The effects of experimental conditions, such as initial pH and concentration of sulfate ion, and ammonia concentration of stripping solution were studied. The extraction percentage of vanadium were increased with the increase of initial pH of leaching solution and decreased with the increase of sulfate ion. More than 99% of vanadium in leaching solution were extracted and stripped at the A/O ratio of 1.0 in 2 stages. On the basis of these results, an optimum solvent extraction process which vanadium was effectively recovered from SCR spent catalyst was proposed.

• Resources Recycling
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• v.29 no.5
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• pp.38-47
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• 2020

In this study, factors affecting the adsorption reaction for the separation/recovery of V and W using Lewatit monoplus MP 600, a strong basic anion exchange resin, from the leachate obtained through the soda roasting-water leaching process from the spent SCR DeNO_X catalyst investigated and the adsorption mechanism was discussed based on the results. In the case of the mixed solution of V and W, both ions showed a high adsorption ratio at pH 2-6, but the adsorption of W was greatly reduced at pH 8. In the adsorption isothermal experiment, both V and W were fitted well at the Langmuir adsorption isotherm, and the reaction kinetics were fitted well at pseudo-second-order. As a result of conducting an adsorption experiment by adjusting the pH with H₂SO₄ to remove Si, which inhibits the adsorption of V and W from the leachate, the lowest W adsorption ratio was shown at pH 8.5. Desorption of W was hardly achieved in strongly acidic solutions, and desorption of V was well performed in both strongly acidic and strongly basic solutions.

• Resources Recycling
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• v.30 no.4
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• pp.54-63
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• 2021

Vanadium and tungsten can be obtained by separating/recovering the leaching solution from a spent SCR DeNO_X catalyst using the soda roasting-water leaching process. Therefore, in this study, the adsorption/desorption mechanism of vanadium and tungsten in an ion-exchange column was investigated using Lewatit MonoPlus MP 600, a strong basic anion exchange resin. The operating conditions for the separation of vanadium and tungsten in the ion-exchange column was intended to present. By conducting a continuous adsorption experiment in a pH 8.5 solution, the adsorption capacity of vanadium and tungsten was found to be 44.75 and 64.92 mg/(g of resin), respectively, which showed that the adsorption capacity of tungsten was larger than that of vanadium because of the difference in ion charge. Vanadium has a higher affinity for MP 600 than tungsten. Consequently, as the vanadium-containing solution is eluted through the ion exchange resin onto which tungsten is adsorbed, the adsorbed tungsten is exchanged with vanadium and desorbed. A continuous experiment was performed with a solution of vanadium and tungsten prepared at the same concentration as the spent SCR DeNO_X catalyst leachate. The adsorption capacity of vanadium was found to be 48.72 mg/(g of resin) and 80% of the supplied vanadium was adsorbed; in contrast, almost no tungsten was adsorbed. Therefore, vanadium and tungsten were separated effectively. The ion exchange resin was treated with 2 M HCl at 15 mL/h, and 97.7% of the vanadium(99% purity) could be desorbed. After desorption, NH₄Cl was added to precipitate ammonium polyvanadate at 90℃ and recover 93% of the vanadium.

• Korean Chemical Engineering Research
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• v.49 no.6
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• pp.739-744
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• 2011

Activated carbon SCR(CSCR) catalyst that is used to remove $NO_x$ in exhaust gas including boron discharged from the production process of liquid crystal display(LCD) shows deactivation when boron is deposited to block the pores within the catalyst or to cover its active sites. The spent carbon catalyst is regenerated by washing with various surfactants, drying and calcination. For comparison of the physical and chemical properties before and after the regeneration with the variables, type of surfactants and calcination condition, element analysis by ICP, $N_{2}$ adsorption were conducted. $DeNO_{x}$ in SCR with $NH_3$ was carried out in a fixed bed reactor at $120^{\circ}C$. The activated carbon catalyst regenerated through washing with a non-ionic surfactant in $H_{2}O$ at $90^{\circ}C$ and calcination under $N_{2}$ gas at $550^{\circ}C$ shows similar level of surface area and $NO_x$ removal efficiency with those of fresh catalyst.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2014.11a
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• pp.94-94
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• 2014

본 연구는 탈질용 폐 SCR 촉매로부터 유가금속인 바나듐과 텅스텐을 회수하기 위하여 고온 소다배소, 수침출, 침전 및 용매추출 실험 순으로 진행하였다. 소다배소는 $Na_2CO_3$ 첨가량 5당량, 폐촉매 평균 입자크기 $54{\mu}m$, 배소온도 $850^{\circ}C$, 배소시간 120분의 조건이 적절하였고, 소다배소 산물의 수침출 실험은 배소산물 입자크기 $-45{\mu}m$, 침출온도 $40^{\circ}C$, 침출시간 30분 및 광액밀도 10%의 조건이 적절하였다. 이와 같은 조건하에서 소다배소 및 수침출 실험을 수행한 결과, 바나듐 성분 약 46%와 텅스텐 성분 약 92%가 침출 되었다. 수침출 공정에서 얻어진 바나듐과 텅스텐이 함께 침출된 침출용액으로부터 바나듐 성분을 선택적으로 침전시키기 위하여 MgCl2를 사용하여 침전실험을 수행하였으나, 바나듐 성분이 침전될 때 텅스텐 성분이 함께 침전되어 큰 손실율을 나타내었다. 또한, 침출용액 내의 바나듐과 텅스텐 성분을 분리하기 위하여 용매추출 실험을 수행하였다. 아민계열의 추출제인 Alamine 336 및 Aliquat 336을 사용한 용매추출 실험에서 바나듐과 텅스텐 성분 모두 90% 이상 추출되었다. 이후 수행된 탈거실험에서 대부분의 역추출제에 의해 바나듐과 텅스텐은 동시에 탈거되었다. 그러나 Alamine 336을 추출제로 사용한 유기상의 탈거실험에서 NaCl 및 NH4Cl 용액을 탈거용액으로 사용하였을 경우에 바나듐과 텅스텐이 선택적으로 탈거될 수 있는 가능성을 나타내었다. 반면에 Aliquat 336을 추출제로 사용한 유기상의 탈거실험의 경우, NaOH 용액이 가장 선택적인 탈거용액임을 확인하였다.

• Resources Recycling
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• v.29 no.5
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• pp.48-54
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• 2020

Sulphuric acid (H₂SO₄) leaching and hydrolysis were experimented for the recovery of titanum dioxide (TiO₂) from the water-leached residue followed by soda-roasting spent SCR catalysts. Sulphuric acid leaching of Ti was carried out with leachate concentration (4~8 M) and the others were fixed (temp.: 70 ℃, leaching time: 3 hrs, slurry density: 100 g/L, stirring speed: 500 rpm). For recovering of Ti from the leaching solution, hydrolysis precipitation was conducted at 100 ℃ for 2 hours in various mixing ratio (leached solution:distilled water) of 1:9 to 5:5. The maximum leachability was reached to 95.2 % in 6 M H₂SO₄ leachate. on the other hand, the leachability of Si decreased dramatically 91.7 to 3.0 % with an increase of H₂SO₄ concentration. Hydrolysis precipitation of Ti was proceeded with leaching solution of 8 M H₂SO₄ with the lowest content of Si. The yield of precipitation increased proportionally with a dilution ratio of leaching solution. Moreover, it increased generally by adding 0.2 g TiO₂ as a precipitation seed to the diluted leaching solution. Ultimately, 99.8 % of TiO₂ can be recovered with the purity of 99.46 % from the 1:9 diluted solution.