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Technical Review of Sulfur Removal Solutions from Oil
- 1. A TECHNICAL REVIEW OF POTENTIAL SOLUTIONS TO CURRENT CHALLENGES OF SULFUR REMOVAL FROM OIL Individual dissertation EG5908 Laura Muniafu ID: 51340565 Supervisor: Prof. J.Anderson Aberdeen, 2015
- 2. Forms of sulphur Pyrite(FeS2) extracted from http://www.mineralminers.com/html/pytmins.stm
- 3. What are the problems caused by sulphur • Environmental challenges • Smog • SO2 (Air pollution) • Acid rain • Soil acidification • Health risks (emphysema, asthma) • Corrosion http://www.themarysue.com/chinese-fire-smog/ http://www.icorr.org/news/180/index.phtml • Catalyst poisoning Poisoning of catalysts used in HDS (Cu/ZnO, Pd, Pt etc) Poisoning of catalysts used in catalytic converters in vehicles.
- 4. Legislation regarding sulphur content in bunker and diesel fuels • MARPOL 73/78 Convention Annex VI • EU Directive 2009/30/EC • Initial EU Directive 93/12/EEC • 98/70/EC • Revised four times to become what it is today.
- 5. What are the challenges of sulphur removal? • High pressure and temperature requirements (350-400° C and high partial pressures i.e. 50atm). • Steric hinderance (from 4-DMDBT and 4,6,DMDBT). • Catalyst configuration/geometry including catalyst support (Ni-Mo catalysts have more hydrogenating abilities than Co-Mo but Co-Mo better at low temperature high pressure conditions. • Type of sulphur compounds present (varying reactivity and selectivity) i.e DBT>4DMDBT>4,6,DMDBT.
- 6. Purposes for desulfurisation 1. Meeting refiners sulphur content specifications 2. Meeting market specifications for sulphur content in crude oil products. 3. Meeting environmental legislation for sulphur compounds emissions including EU Directive 2009/30/EC , MARPOL 73/78 Annex VI and Clean Air Amendment Act. 4. Reduce corrosion problems when transporting crude oil from upstream, midstream and downstream. 5. Prevent catalyst poisoning by sulphur compounds
- 7. Options available for deep desulfurisation 1. Hydrodesulphurization - hydrogen intensive methods 2. Non- hydrodesulphurization – which do not utilize hydrogen • Oxidative desulfurisation (UOAD, photochemical oxidative desulfurisation coupled with ionic liquid extraction (PODS-IL), desulfurisation with molecular oxygen in presence of a catalyst), ODS with acid catalysts and strong oxidant) • Biodesulfurisation • Extractive desulfurisation (desulfurisation by ionic liquids, alkali metal compounds) • Adsorptive desulfurisation • Desulfurisation by chlorinolysis • Desulfurisation by super-critical water (SCW)
- 8. Oxidative desulfurisation • Advantages • Can be complimentary to HDS • Involves oxidation and extraction processes • Utilises cheap reactants • Mild reactor conditions in comparison to HDS Challenges include; Limited availability of peroxides and increased costs. Typical oxidative desulfurisation reaction Hielschars ultrasonic assisted oxidative desulfurisation process
- 9. Biodesulfurisation • Advantages • Environmentally friendly technology • Mild operating conditions • Promising degree of desulfurisation (65-76%)] when applied alone. • High degree of desulfurisation (upto 92%) when BDS is coupled with other desulfurisation methods. • biocatalyst lifetime (200-400hours) • Disadvantages • Challenges include sanitary handling and shipment, storage and use of living bacterial. • Commercialisation. • Further improvement on key engineering elements such as reactor design, oil/water/biocatalyst separation, disposal of the byproducts and product quality.
- 10. Extractive desulfurisation(ionic liquids, alkali metals etc) • Advantages • Mild reaction conditions/low temperature and pressure requirements • Non-complex process and can easily be integrated into existing refineries. • Sulphur may be removed by water washing. • 50-90% sulphur removal Disadvantages • Efficiency limited by solubility of organosulphur compounds. • Appropriate solvent selection is required. • Challenges in solvent recovery (ILs)
- 11. Desulfurisation by chlorinolysis • Mild reaction conditions/low temperature and pressure requirements (25-80°C) • Has achieved high degree of desulfurisation efficiency (75-90%) within a short time period . • Can be applied both upstream and downstream RSCl H2O RSO2Cl H2O , Cl2 RCl + SO4 2− Chlorinolysis reaction as defined by kalvinskas et al.
- 12. Adsorptive desulfurisation • Advantages • High degree of desulfurisation efficiency (>90%) • Mild reactor conditions • Able to remove refractory sulphur compounds. PSU-SARS reactor design • Disadvantages • Limitations on sorbent selectivity, adsorption capacity, durability and regenerability. • High sorbent requirement for effective desulfurisation
- 13. Conclusions • Non hydrogen based desulfurisation methods (ODS, BDS, ECOD, etc)offer plausible alternatives to sulphur removal • Challenge of commercialisation. • Further work being done by scientists and researchers on making them more commercially viable.
- 14. Bibliography • Halliburton, 2005. Paraffin and Asphaltene Control. [Online] Available at: http://www.halliburton.com/public/pe/contents/Brochures/Web/H04347.pdf [Accessed 28th February 2015]. • Kamran Akbarzadeh, A. H. K., 2007. Asphaltenes—Problematic but Rich in Potential. Oilfield Review, pp. 22-43. • Kilpatrick, X. Y. a. P., 2005. Asphaltenes and Waxes Do Not Interact Synergistically and Coprecipitate in 4. Solid Organic Deposits. Energy & Fuels, Issue 19, pp. 1360-1375. • Mansoori, G. A., 2010. Remediation of Asphaltene and other Heavy Organic Deposits in Oil Wells and in Pipelines. s.l., SOCAR. • Petrowiki, 2013. Thermodynamic models for Asphaltene precipitation. [Online] Available at: http://petrowiki.org/Thermodynamic_models_for_asphaltene_precipitation [Accessed 28 February 2015].