Commenced in January 2007
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Edition: International
Paper Count: 10

desulfurization Related Abstracts

10 Extractive Desulfurization of Atmospheric Gasoil with N,N-Dimethylformamide

Authors: Kahina Bedda, Boudjema Hamada


Environmental regulations have been introduced in many countries around the world to reduce the sulfur content of diesel fuel to ultra low levels with the intention of lowering diesel engine’s harmful exhaust emissions and improving air quality. Removal of sulfur containing compounds from diesel feedstocks to produce ultra low sulfur diesel fuel by extraction with selective solvents has received increasing attention in recent years. This is because the sulfur extraction technologies compared to the hydrotreating processes could reduce the cost of desulfurization substantially since they do not demand hydrogen, and are carried out at atmospheric pressure. In this work, the desulfurization of distillate gasoil by liquid-liquid extraction with N, N-dimethylformamide was investigated. This fraction was recovered from a mixture of Hassi Messaoud crude oils and Hassi R'Mel gas-condensate in Algiers refinery. The sulfur content of this cut is 281 ppm. Experiments were performed in six-stage with a ratio of solvent:feed equal to 3:1. The effect of the extraction temperature was investigated in the interval 30 ÷ 110°C. At 110°C the yield of refined gas oil was 82% and its sulfur content was 69 ppm.

Keywords: desulfurization, gasoil, N-dimethylformamide, sulfur content

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9 Synthesis, Characterization, and Application of Novel Trihexyltetradecyl Phosphonium Chloride for Extractive Desulfurization of Liquid Fuel

Authors: Swapnil A. Dharaskar, Kailas L. Wasewar, Mahesh N. Varma, Diwakar Z. Shende


Owing to the stringent environmental regulations in many countries for production of ultra low sulfur petroleum fractions intending to reduce sulfur emissions results in enormous interest in this area among the scientific community. The requirement of zero sulfur emissions enhances the prominence for more advanced techniques in desulfurization. Desulfurization by extraction is a promising approach having several advantages over conventional hydrodesulphurization. Present work is dealt with various new approaches for desulfurization of ultra clean gasoline, diesel and other liquid fuels by extraction with ionic liquids. In present paper experimental data on extractive desulfurization of liquid fuel using trihexyl tetradecyl phosphonium chloride has been presented. The FTIR, 1H-NMR, and 13C-NMR have been discussed for the molecular confirmation of synthesized ionic liquid. Further, conductivity, solubility, and viscosity analysis of 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 dibenzothiphene from liquid fuel were also investigated. In extractive desulfurization process, the removal of dibenzothiophene in n-dodecane was 84.5% for mass ratio of 1:1 in 30 min at 30OC 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.

Keywords: Extraction, liquid fuel, desulfurization, ionic liquid, PPIL

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8 Adsorptive Desulfurization of Tire Pyrolytic Oil Using Cu(I)–Y Zeolite via π-Complexation

Authors: Moshe Mello, Hilary Rutto, Tumisang Seodigeng


The accelerating requirement to reach 0% sulfur content in liquid fuels demands researchers to seek efficient alternative technologies to challenge the predicament. In this current study, the adsorption capabilities of modified Cu(I)-Y zeolite were tested for removal of organosulfur compounds (OSC) present in TPO. The π-complexation-based adsorbent was obtained by ion exchanging Y-zeolite with Cu+ cation using liquid phase ion exchange (LPIE). Preparation of the adsorbent involved firstly ion-exchange between Na-Y zeolite with a Cu(NO3)2 aqueous solution of 0.5M for 48 hours followed by reduction of Cu2+ to Cu+. Batch studies for TPO in comparison with model diesel comprising of sulfur compounds such as thiophene (TH), benzothiophene (BTH), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophe (4,6-DMDBT) showed that modified Cu(I)-Y zeolite is an effective adsorbent for removal of OSC in liquid fuels. The effect of multiple operating conditions such as adsorbent dosage, reaction time and temperature were studied to optimize the process. For model diesel fuel, the selectivity for adsorption of sulfur compounds followed the order 4,6-DMDBT> DBT> BTH> TH. Interpretation of the results was justified using the molecular orbital theory and calculations. Langmuir and Freundlich isotherms were used to predict adsorption of the reaction mixture. The Cu(I)-Y zeolite is fully regeneratable and this is achieved by a simple procedure of blowing the adsorbent with air at 350 °C, followed by reactivation at 450 °C in a rich helium surrounding.

Keywords: Adsorption, Zeolite, desulfurization, TPO

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7 Extractive Desulfurization of Fuels Using Choline Chloride-Based Deep Eutectic Solvents

Authors: T. Zaki, Fathi S. Soliman


Desulfurization process is required by most, if not all refineries, to achieve ultra-low sulfur fuel, that contains less than 10 ppm sulfur. A lot of research works and many effective technologies have been studied to achieve deep desulfurization process in moderate reaction environment, such as adsorption desulfurization (ADS), oxidative desulfurization (ODS), biodesulfurization and extraction desulfurization (EDS). Extraction desulfurization using deep eutectic solvents (DESs) is considered as simple, cheap, highly efficient and environmentally friend process. In this work, four DESs were designed and synthesized. Choline chloride (ChCl) was selected as typical hydrogen bond acceptors (HBA), and ethylene glycol (EG), glycerol (Gl), urea (Ur) and thiourea (Tu) were selected as hydrogen bond donors (HBD), from which a series of deep eutectic solvents were synthesized. The experimental data showed that the synthesized DESs showed desulfurization affinities towards the thiophene species in cyclohexane solvent. Ethylene glycol molecules showed more affinity to create hydrogen bond with thiophene instead of choline chloride. Accordingly, ethylene glycol choline chloride DES has the highest extraction efficiency.

Keywords: Extraction, DES, desulfurization, green solvent

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6 Improvement of Diesel Oil Properties by Batch Adsorption and Simple Distillation Processes

Authors: M. Firoz Kalam, Wilfried Schuetz, Jan Hendrik Bredehoeft


In this research, diesel oil properties, such as aniline point, density, diesel index, cetane index and cetane number before and after treatment were studied. The investigation was considered for diesel oil samples after batch adsorption process using powdered activated carbon. Batch distillation process was applied to all treated diesel oil samples for separation of the solid-liquid mixture. The diesel oil properties were studied to observe the impact of adsorptive desulfurization process on fuel quality. Results showed that the best cetane number for desulfurized diesel oil was found at the best-operating conditions 60℃, 10g activated carbon and 180 minute contact time. The best-desulfurized diesel oil cetane number was obtained around 51 while the cetane number of untreated diesel oil was 34. Results also showed that the calculated cetane number increases as the operating temperature and amounts of adsorbent increases. This behavior was same for other diesel oil properties such as aniline point, diesel index, cetane index and density. The best value for all the fuel properties was found at same operating conditions mentioned above. Thus, it can be concluded that adsorptive desulfurization using powdered activated carbon as adsorbent had significantly improved the fuel quality of diesel oil by reducing aromatic contents of diesel oil.

Keywords: Adsorption, activated carbon, desulfurization, fuel quality, diesel oil

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5 Simulation of Wet Scrubbers for Flue Gas Desulfurization

Authors: Anders Schou Simonsen, Kim Sorensen, Thomas Condra


Wet scrubbers are used for flue gas desulfurization by injecting water directly into the flue gas stream from a set of sprayers. The water droplets will flow freely inside the scrubber, and flow down along the scrubber walls as a thin wall film while reacting with the gas phase to remove SO₂. This complex multiphase phenomenon can be divided into three main contributions: the continuous gas phase, the liquid droplet phase, and the liquid wall film phase. This study proposes a complete model, where all three main contributions are taken into account and resolved using OpenFOAM for the continuous gas phase, and MATLAB for the liquid droplet and wall film phases. The 3D continuous gas phase is composed of five species: CO₂, H₂O, O₂, SO₂, and N₂, which are resolved along with momentum, energy, and turbulence. Source terms are present for four species, energy and momentum, which are affecting the steady-state solution. The liquid droplet phase experiences breakup, collisions, dynamics, internal chemistry, evaporation and condensation, species mass transfer, energy transfer and wall film interactions. Numerous sub-models have been implemented and coupled to realise the above-mentioned phenomena. The liquid wall film experiences impingement, acceleration, atomization, separation, internal chemistry, evaporation and condensation, species mass transfer, and energy transfer, which have all been resolved using numerous sub-models as well. The continuous gas phase has been coupled with the liquid phases using source terms by an approach, where the two software packages are couples using a link-structure. The complete CFD model has been verified using 16 experimental tests from an existing scrubber installation, where a gradient-based pattern search optimization algorithm has been used to tune numerous model parameters to match the experimental results. The CFD model needed to be fast for evaluation in order to apply this optimization routine, where approximately 1000 simulations were needed. The results show that the complex multiphase phenomena governing wet scrubbers can be resolved in a single model. The optimization routine was able to tune the model to accurately predict the performance of an existing installation. Furthermore, the study shows that a coupling between OpenFOAM and MATLAB is realizable, where the data and source term exchange increases the computational requirements by approximately 5%. This allows for exploiting the benefits of both software programs.

Keywords: desulfurization, scrubber, discrete phase, wall film

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4 A Comparative Assessment of Membrane Bioscrubber and Classical Bioscrubber for Biogas Purification

Authors: Ebrahim Tilahun, Erkan Sahinkaya, Bariş Calli̇


Raw biogas is a valuable renewable energy source however it usually needs removal of the impurities. The presence of hydrogen sulfide (H2S) in the biogas has detrimental corrosion effects on the cogeneration units. Removal of H2S from the biogas can therefore significantly improve the biogas quality. In this work, a conventional bioscrubber (CBS), and a dense membrane bioscrubber (DMBS) were comparatively evaluated in terms of H2S removal efficiency (RE), CH4 enrichment and alkaline consumption at gas residence times ranging from 5 to 20 min. Both bioscrubbers were fed with a synthetic biogas containing H2S (1%), CO2 (39%) and CH4 (60%). The results show that high RE (98%) was obtained in the DMBS when gas residence time was 20 min, whereas slightly lower CO2 RE was observed. While in CBS system the outlet H2S concentration was always lower than 250 ppmv, and its H2S RE remained higher than 98% regardless of the gas residence time, although the high alkaline consumption and frequent absorbent replacement limited its cost-effectiveness. The result also indicates that in DMBS when the gas residence time increased to 20 min, the CH4 content in the treated biogas enriched upto 80%. However, while operating the CBS unit the CH4 content of the raw biogas (60%) decreased by three fold. The lower CH4 content in CBS was probably caused by extreme dilution of biogas with air (N2 and O2). According to the results obtained here the DMBS system is a robust and effective biotechnology in comparison with CBS. Hence, DMBS has a better potential for real scale applications.

Keywords: Biogas, desulfurization, bioscrubber, PDMS membrane

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3 Optimization of Effecting Parameters for the Removal of H₂S Gas in Self Priming Venturi Scrubber Using Response Surface Methodology

Authors: Manisha Bal, B. C. Meikap


Highly toxic and corrosive gas H₂S is recognized as one of the hazardous air pollutants which has significant effect on the human health. Abatement of H₂S gas from the air is very necessary. H₂S gas is mainly released from the industries like paper and leather industry as well as during the production of crude oil, during wastewater treatment, etc. But the emission of H₂S gas in high concentration may cause immediate death while at lower concentrations can cause various respiratory problems. In the present study, self priming venturi scrubber is used to remove the H₂S gas from the air. Response surface methodology with central composite design has been chosen to observe the effect of process parameters on the removal efficiency of H₂S. Experiments were conducted by varying the throat gas velocity, liquid level in outer cylinder, and inlet H₂S concentration. ANOVA test confirmed the significant effect of parameters on the removal efficiency. A quadratic equation has been obtained which predicts the removal efficiency very well. The suitability of the developed model has been judged by the higher R² square value which obtained from the regression analysis. From the investigation, it was found that the throat gas velocity has most significant effect and inlet concentration of H₂S has less effect on H₂S removal efficiency.

Keywords: Pollution control, response surface methodology, desulfurization, venturi scrubber

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2 Metal-Based Deep Eutectic Solvents for Extractive Desulfurization of Fuels: Analysis from Molecular Dynamics Simulations

Authors: Aibek Kukpayev, Dhawal Shah


Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.

Keywords: Molecular Dynamics Simulations, desulfurization, deep eutectic solvents, thiophenes

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1 Bayesian Optimization for Reaction Parameter Tuning: An Exploratory Study of Parameter Optimization in Oxidative Desulfurization of Thiophene

Authors: Aman Sharma, Sonali Sengupta


The study explores the utility of Bayesian optimization in tuning the physical and chemical parameters of reactions in an offline experimental setup. A comparative analysis of the influence of the acquisition function on the optimization performance is also studied. For proxy first and second-order reactions, the results are indifferent to the acquisition function used, whereas, while studying the parameters for oxidative desulphurization of thiophene in an offline setup, upper confidence bound (UCB) provides faster convergence along with a marginal trade-off in the maximum conversion achieved. The work also demarcates the critical number of independent parameters and input observations required for both sequential and offline reaction setups to yield tangible results.

Keywords: Kinetics, Bayesian Optimization, thiophene, desulfurization, acquisition function

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