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Transcript of 145 swapnil
IONIC LIQUIDS:- ENERGY EFFICIENT GREEN SOLVENT FOR THE EXTRACTIVE DESULFURIZATION OF LIQUID
FUELS
Mr. Swapnil A. DharaskarResearch Scholar
Under Supervision
Dr. Kailas L. Wasewar&
Dr. Mahesh N. Varma
Department of Chemical EngineeringVisvesvaraya National Institute of Technology (VNIT)
Nagpur – 440010, Maharashtra, INDIA
4th International Conference on Advances in Energy Research
ICEAR-2013Indian Institute of Technology
Mumbai (M.S) India.
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Objective
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Imidazolium Pyridinium Phosphonium Sulfonium
1-butyl-3-methylimidazolium Chloride
1-butyl-3-methylimidazolium Bromide
1-butyl-3-methylimidazolium Tetrafluoroborate
1-butyl-3-methylimidazolium Hexafluorophosphate
Ammonium
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Why Extractive desulfurization?
In petroleum and hydrocarbon industries, various solvents such as ethers, amines, alcohols and other volatile organic compounds have been used for the options like extraction, absorption, azeotropic distillation etc.
These solvents have their own limitations in terms of environmental issue, recycle ability, etc. which can be overcome by the use of ionic liquids as green solvent.
Among theses EDS seems more eye-catching because it does not require hydrogen and catalyst and its operation conditions is mild.
Moreover, it does not alter the chemical structures of the compounds in fuel oils and extracted S-compounds can be reused as raw materials.
A good extractant much have the following attributes:-a) Good extractive ability for S-compounds.b) Free of contamination to the fuels.c) Non-toxicity, and environmental benignity.d) Stability for repetitive use
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Basic concept of Desulfurization
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FT-IR analysis of ionic liquids
1H-NMR and 13C-NMR analysis
Thermal Analysis
Conductivity Analysis
Solubility Analysis
Viscosity Analysis
Characterization of ILs
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A model liquid fuel with 500 ppmw sulfur (DBT as sulfur source) was prepared in n-Octane. Similarly, the model liquid fuels were prepared by dissolving BT, T, and 3-MT individually in n-Octane respectively. Actual diesel and gasoline with total sulfur content of 385.13 and 180.79 ppmw respectively were used.
Results and Discussion
Preparation of Model Fuel
Effect of Reaction Time on S-removal
Effect of Reaction Temperature on S-removal
Effect of S-Compound on S-removal.
Recycling of spent ILs without Regeneration.
Desulfurization of Real Fuels using imidazolium IL
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Effect of reaction time on DBT removal with IL
IL Time (min)
S-content(ppmw)
S-removal
(%)
Part. Coeff.(KN)
[BMIM]BF4
5 214.55 57 1.3310 199.05 60.2 1.5120 184.55 63 1.7130 170.05 66 1.94
[BMIM]PF6
5 223.55 55.3 1.2410 209.55 58 1.3920 194.05 61.2 1.5830 181.5 63.7 1.75
Temperature = 30OC, Mass ratio of model fuel/IL = 5:1, Extraction time = 30 min. Initial sulfur concentration = 500 ppmw.
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Effect of reaction temperature on S-removal with IL
IL Temperature (OC)
S-content(ppmw)
S-removal
(%)
Part. Coeff.(KN)
[BMIM]BF4
20 198.5 60.3 1.5225 179.05 64.2 1.7935 165.05 67 2.0245 224.55 55 1.2255 263.55 47.3 0.89
[BMIM]PF6
20 213.05 57.4 1.3525 200.05 60 1.535 171.5 65.7 1.9245 249.05 50.2 1.055 279.55 44 0.79
Temperature = 30OC, Mass ratio of model fuel/IL = 5:1, Extraction time = 30 min. Initial S-concentration = 500 ppmw.
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Effect of S-compound on DBT removal
Reactivity sequencing was DBT > BT > T > 3-MT.
IL S-Compoun
d
S- conten
t(ppmw
)
S-remova
l (%)
Part. Coeff.(KN)
IL S- content(ppmw)
S-removal
(%)
Part. Coeff.(KN)
[BMIM]BF4DBT 169.5
566 1.94
[BMIM]PF6
174.09 65.2 1.87
BT 180.49
63.9 1.77 210.39 57.9 1.37
T 231.09
53.8 1.16 250.19 49.9 0.99
3-MT 260.30
47.9 0.92 285.79 42.8 0.75
Temperature = 30OC, Mass ratio of model fuel/IL = 3:1, Extraction time = 30 min. Initial sulfur concentration = 500 ppmw.
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Recycling of spent ILs without regeneration
No. of Cycle IL S-removal (%)1
[BMIM]BF4
662 55.43 48.54 361
[BMIM]PF6
63.72 53.43 45.24 31
Model fuel = (n-Octane + DBT), Mass ratio of model fuel/IL = 5:1, Temperature = 30OC, Extraction time = 30 min, Initial S-concentration = 500 ppmw.
Desulfurization of Real Fuels using ILs
IL Diesel/IL(Mass Ratio)
S-conten
t(ppmw
)
S-remova
l(%)
Part. Coeff.(KN)
Gasoline/IL
(Mass Ratio)
S-conten
t(ppmw
)
S-remov
al(%)
Part. Coeff.(KN)
[BMIM]BF4
5:1 210.31
45.4 0.83 5:1 70.2 61.1 0.61
[BMIM]PF6
225.19
41.5 0.71 90.3 50 1.0
Temperature = 30OC, Extraction time = 30 min, Initial S-concentration of diesel and gasoline = 385.13 and 180.79 ppmw.
Multistage Extraction Process
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Conclusion
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Highlights
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Imidazolium based (ILs) were synthesized and employed as an Extractant for S-removal.
Imidazolium Ils can be used as energy efficient green material for EDS of liquid fuels, mainly with regards to those S-compounds that are very complex to remove by common hydrodesulfurization (HDS) technique.
The spent IL could be reused for four times with a slight decrease in activity.
Enormous saving on energy can be achieved by use of IL in process.
This work could be present a new alternative for extractive deep-desulfurization of liquid fuels.
The EDS method could be option for environmentally benign method for deep desulfurization.
Application of ILs
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Analytical Equipments Used
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• Fourier Transform Infra Red (FTIR).• Nuclear magnetic resonance (NMR)• Differential Scanning Calorimetry (DSC).• Thermogravimetric Analysis (TG/DTA).• Thermo-scientific Total Sulfur Analyzer (TS-
3000).• Inductively coupled plasma-AES• X-ray fluorescence spectrophotometer (XRF)• UV visible Spectrophotometer.• Gas Chromatography with mass spectometry
(GC-MS)High Pressure Liquid Chromatography (HPLC).
Acknowledgements
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CSIR VNIT, Nagpur
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