Hydrometallurgical process development for the extraction, separation and recovery of vanadium from spent desulfurization catalyst bio-leach liquors

Kim, Hong-In,Moon, Gyeonghye,Choi, Inhyeok,Lee, Jin-Young,Jyothi, Rajesh Kumar Elsevier 2018 Journal of cleaner production Vol.187 No.-

<P><B>Abstract</B></P> <P>The processes of vanadium extraction, separation and recovery from spent de-sulfurization catalyst bio-leach liquor solutions were studied. Spent catalyst processing has mainly two benefits: to protect the environment from the effects of waste and to create wealth from waste. Numerous experimental parameters are optimized. The first step evaluated possible suitable extractant systems, followed by the optimal pH conditions. Feasible extractant systems were screened in the first step. The commercial extractants of LIX 973N, Alamine 336, Alamine 308, Cyanex 272 and D2EHPA were examined. In this study, the initial pH varied from 0.0 to 2.5, and after extraction equilibrium, the measured pH was between 0.1 and 2.8. The developed process involves an examination of the phase ratio effect, the creation of a McCabe–Thiele diagram to extract the isotherm, and counter-current extraction (CCE), all of which were examined and optimized for vanadium. The McCabe–Thiele plots showed that quantitative extraction of the target metal was achievable in extraction stages. The CCE process further confirmed the maximum loading of the vanadium while minimizing interference from other metals. Other processes such as scrubbing and stripping were also established. Hydrochloric acid diluted with water was used as a scrubbing reagent, and its pH was 0.8 ± 0.1. Metal enrichment was achieved at a fivefold greater rate by a continuous counter-current extraction process and finally with ammonium hydroxide, with a vanadium amount as high as much as (2039 mg/L) recovered from a loaded organicphase (5180 mg/L).</P> <P><B>Highlights</B></P> <P> <UL> <LI> Process developed for vanadium recovery from spent desulfurization catalyst (SDC). </LI> <LI> This study found that for V; best suitable extractants were amine based extractants. </LI> <LI> McCabe–Thiele diagrams concluded that A/O ratios 5, 5.5 and 6 were optimized. </LI> <LI> Counter-current extraction process generated maximum loaded organic of Alamine 308. </LI> <LI> Process development study concludes that, Alamine 308 is the better than 336. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>Process development for vanadium recovery from spent desulfurization catalyst leach liquors.</P> <P>[DISPLAY OMISSION]</P>

Extractive-oxidative removals of dibenzothiophene and quinoline using vanadium substituted Dawson emulsion catalyst and ionic liquid based solvents

F. Banisharif,M.R. Dehghani,M.C. Capel-Sanchez,J.M. Campos-Martin 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.47 No.-

Extractive-catalytic oxidative desulfurization (ECODS) of model diesel using vanadium substitutedDawson-type emulsion catalyst has been investigated for thefirst time. At different operationalconditions, ECODS was studied using selected solvents and [cetrimonium]11P2W13V5O62 by means ofTaguchi methods Under the optimized conditions (ionic liquids/oil volume ratio 1:8, 7.5 g/L catalyst, O/Smole ratio 8, T = 70 C after 45 min) 94% of sulfur and 100% of quinoline were removed. It is worthmentioning that in the presence of catalyst, solvent/oil volume decreases by 45% while sulfur removalincreases by 54% compared to extraction desulfurization.

석유 코크스에 함유된 황 성분의 직접 탈황: 용매 추출 및 고온 열처리 비교

박노국,송유나,부진호,이승우,김민규,이승종,윤용승 한국에너지기후변화학회 2022 에너지기후변화학회지 Vol.17 No.2

In this study, the possibility of direct desulfurization technology as a pretreatment technology to reduce theconcentration of sulfur compounds contained in syngas produced from the gasification of petroleum coke wasexperimentally investigated. High-temperature thermal treatment and solvent extraction were applied as directdesulfurization techniques for petroleum cokes. The weight changes due to volatilization of free sulfur above 250 °C wasconfirmed by TGA analysis. When the thermal treatment of petroleum coke powder was performed in the range of250-330 °C, sulfur volatilization with high yield above 330 °C was confirmed by SEM / EDX analysis. In addition, it wasconfirmed by UV-Visible adsorption spectrum and FT-IR analysis that organic sulfur contained in petroleum coke wasextracted with using ethanol, acetone, and polyethylene glycol as solvents. Although the effect of direct desulfurizationis not high by thermal treatment and solvent extraction, it was considered to be effective as a pretreatment method toreduce the concentration load of sulfur compound gases in syngas produced from petroleum cokes derived gasification. In the future, it was expected to contribute to the expansion of mass hydrogen production technology by developing apretreatment process technology to reduce sulfur content in petroleum coke by direct desulfurization.

Synthesis, characterization and application of 1-butyl-3-methylimidazolium tetrafluoroborate for extractive desulfurization of liquid fuel

Dharaskar, S.A.,Wasewar, K.L.,Varma, M.N.,Shende, D.Z.,Yoo, C. Elsevier ; King Saud University 2016 Arabian journal of chemistry Vol.9 No.4

<P>In the present paper the experimental data of extractive desulfurization of liquid fuel using 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM]BF4 have been presented. The data of FTIR, 1 H NMR and C-13 NMR have been discussed for the molecular confirmation of synthesized [BMIM]BF4. Further, the thermal properties, conductivity, solubility, and viscosity analysis of the [BMIM]BF4 were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of ionic liquid without regeneration on dibenzothiophene removal of liquid fuel were presented. In extractive desulfurization process, the removal of dibenzothiophene in n-dodecane was 73.02% for mass ratio of 1: 1 in 30 min at 30 degrees C under the mild reaction conditions. The ionic liquids could be reused four times without a significant decrease in activity. Also, the desulfurizations of real fuels, multistage extraction were presented. The data and results provided in the present paper explore the significant insights of imidazoled ILs for extractive desulfurization of liquid fuels. (C) 2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.</P>

Synthesis, characterization, and application of novel trihexyl tetradecyl phosphonium bis (2,4,4-trimethylpentyl) phosphinate for extractive desulfurization of liquid fuel

Dharaskar, S.A.,Wasewar, K.L.,Varma, M.N.,Shende, D.Z.,Tadi, K.K.,Yoo, C.K. Elsevier Scientific Pub. Co 2014 Fuel processing technology Vol.123 No.-

In present paper experimental data on extractive desulfurization of liquid fuel using trihexyl tetradecyl phosphonium bis (2,4,4-trimethyl pentyl) phosphinate has been presented. The FTIR, <SUP>1</SUP>H NMR, <SUP>13</SUP>C NMR, <SUP>31</SUP>P NMR, and ESR have been discussed for the molecular confirmation of synthesized phosphonium based ionic liquid. Further, conductivity, solubility, and viscosity analyses of phosphonium ionic liquids were carried out. The effects of reaction time, reaction temperature, sulfur compounds, ultrasonication, and recycling of ionic liquid without regeneration on removal of dibenzothiophene from liquid fuel were also investigated. In extractive desulfurization process, the removal of dibenzothiophene in n-dodecane was 79.5% for mass ratio of 1:1 in 30min at 30<SUP>o</SUP>C under the mild reaction conditions. Phosphonium ionic liquids could be reused five times without a significant decrease in activity. Also, the desulfurization of real fuels, multistage extraction was examined. The data and results provided in present paper explore the significant insights of phosphonium based ionic liquids as novel extractant for extractive desulfurization of liquid fuels.

Optimization of extractive desulfurization of Malaysian diesel fuel using response surface methodology/Box–Behnken design

Wan Nur Aini Wan Mokhtar,Wan Azelee Wan Abu Bakar,Rusmidah Ali,Abdul Aziz Abdul Kadir 한국공업화학회 2015 Journal of Industrial and Engineering Chemistry Vol.30 No.-

Systematic experiments were conducted to investigate the most appropriate extraction conditions forsulfur reduction. Initial extraction studies showed that DMF was the most potentially effective solvent. The influence of DMF to diesel ratios, extraction times and temperatures, addition of co-solvent, solventmixtures, double extractions were explored. The use of co-solvent and solvent mixtures showed poorefficiencies of sulfur removal. A two-stage extraction with ratio of 1:1 (DMF/Diesel) was successfullyremoved over 88.0% of sulfur in diesel. Under Box–Behnken design, the model showed that maximumextraction ability was observed at 30 8C, 30 min and 1.0 of DMF/diesel ratio to achieved 67.5%.

Extraction conditions for removal of oxidized sulfur compounds in gas oil

Ali Akbar Safekordi,Mahsa Heidari,Maryam Ghaedian,Amin Shafeghat 한국화학공학회 2013 Korean Journal of Chemical Engineering Vol.30 No.3

An experimental study was conducted to investigate the extraction of oxidized sulfur compounds from gas oil. Solvents used for this purpose included acetone, acetonitrile, methanol and propanol. The effect of solvent concentration,solvent to gas oil ratio, temperature, time and number of stages was studied. To select the best solvent and conditions for extraction, two criteria were considered: high desulfurization and more hydrocarbon recovery. Results showed that extraction time and temperature have no significant effect. Methanol for low ability of extraction of oxidized sulfur compounds and propanol for low hydrocarbon recovery were excluded from further experiments. After the tests,the optimum conditions for extraction were determined to be 85% acetone, solvent/feed ratio of 1, two stages extraction in ambient temperature and enough time for mixing. In this condition 85% of sulfur compounds of gas oil containing 1,670 ppmw S were separated and 95% of gas oil was recovered.

Deep Desulfurization of Fuels by Heteropolyanion-Based Ionic Liquid

Li, Jinlei,Hu, Bing,Hu, Chuanqun Korean Chemical Society 2013 Bulletin of the Korean Chemical Society Vol.34 No.1

A new heteropolyanion-based ionic ($[Hmim]_5PMo_{10}V_2O_{40}$) was synthesized by the reaction of molybdovanadophosphoric acid ($H_5PMo_{10}O_{40}$) with N-methylimidazole. [$[Hmim]_5PMo_{10}V_2O_{40}$ showed a high catalytic activity in the oxidative desulfurization of sulfur-containing compounds in 1-methylimidazolium tetrafluoroborate ($[Hmim]BF_4$) ionic liquid using 30% aqueous $H_2O_2$ as the oxidant. The catalytic system was of high activity, simplified workup and flexible recyclability. The catalytic oxidation reactivity of sulfur-containing compounds decreased in the order dibenzothiophene (DBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The influences of various parameters including reaction time (t) and temperature (T), catalyst dosage, and oxidant to sulfur molar ratio n(O)/n(S) on the desulfurization of model oil were investigated in details. 99.1% of DBT conversion in the model oil was achieved at atmospheric pressure under the optimal conditions: n(O)/n(S) = 4:1, $60^{\circ}C$, 100 min and molar ratio of catalyst to sulfur of 0.062. The ionic liquid can be recycled six times without significant decrease in activity.

Deep Desulfurization of Fuels by Heteropolyanion-Based Ionic Liquid

Jinlei Li,Bing Hu,Chuanqun Hu 대한화학회 2013 Bulletin of the Korean Chemical Society Vol.34 No.1

A new heteropolyanion-based ionic ([Hmim]5PMo10V2O40) was synthesized by the reaction of molybdovanadophosphoric acid (H5PMo10O40) with N-methylimidazole. [Hmim]5PMo10V2O40 showed a high catalytic activity in the oxidative desulfurization of sulfur-containing compounds in 1-methylimidazolium tetrafluoroborate ([Hmim]BF4) ionic liquid using 30% aqueous H2O2 as the oxidant. The catalytic system was of high activity, simplified workup and flexible recyclability. The catalytic oxidation reactivity of sulfur-containing compounds decreased in the order dibenzothiophene (DBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The influences of various parameters including reaction time (t) and temperature (T), catalyst dosage, and oxidant to sulfur molar ratio n(O)/n(S) on the desulfurization of model oil were investigated in details. 99.1% of DBT conversion in the model oil was achieved at atmospheric pressure under the optimal conditions: n(O)/n(S) = 4:1, 60 oC, 100 min and molar ratio of catalyst to sulfur of 0.062. The ionic liquid can be recycled six times without significant decrease in activity.

Deep eutectic solvents based on choline chloride and ethylene glycol as media for extractive denitrification/desulfurization/dearomatization of motor fuels

Marko Rogoši,Kristina Zagajski Ku9can 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.72 No.-

In an attempt to develop alternative methods that meet the criteria of ‘green’ technology in gasolineproduction, choline chloride and ethylene glycol (ChCl-EG) based deep eutectic solvents (DESs) in molarratios of 1:2, 1:3 and 1:3.5 were tested for desulfurization, denitrification and dearomatization of modeland real gasoline. Using ChCl-EG 1:3.5 denitrification efficiency of 70.9% with respect to pyridine wasachieved in a single extraction stage; efficiency above 99% was obtained in four stages. The DESs wereregenerated by evaporating extracted components between stages, allowing for its multiple use. Theequilibrium phase compositions in model fuel experiments were fairly predicted by UNIQUAC model. Physical properties of DESs important for application as extraction solvents were determined, too. Theextraction data collected on real fuels shown that only the loose qualitative correlation with the modelfuel experiments can be established.