Day 1 :
Baker Hughes a GE Company, USA
Valery Khabashesku obtained his professorial Doctor of Science Degree and Doctoral CSc Degree from Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences in, and MSc Degree in Chemistry from Lomonosov Moscow State University, Moscow, Russia respectively. At present, he is a Senior Technical Advisor for Nanotechnology at Baker Hughes a GE Company, one of the world-leading oil field services companies He is also an Adjunct Professor in the Department of Materials Science and Nanoengineering at Rice University; has been a Faculty Member in the Chemistry Department at the same university; Faculty Member- Department of Chemical & Biomolecular Engineering at the University of Houston, USA respectively. He has authored more than 300 publications and has been serving as an editorial board member for the journals of nanotechnology and materials.
Statement of the Problem: Fluorescent nanoparticles are becoming high demand products in the oil industry for application as tracers for reservoir monitoring to understand the flow pattern between the wells during waterflood operations and optimize the oil production. The common tracers, based on organic dyes, are not stable in harsh downhole conditions and are difficult to incorporate. Fluorescent carbon-based nanoparticles ??? carbon quantum dots (CQD) have recently drawn much attention due to outstanding fluorescence properties and pending applications towards chemical sensing and bio imaging. In most cases, CQDs outperform the traditional semiconductor-based quantum dots. They are also inherently non-toxic and stable in high temperature and pH conditions and are resistant to photobleaching. Purpose: The purpose of this study is development of low cost and scalable methods for synthesis of fluorescent carbon-based nanoparticles from petrochemical precursors. Methodology & Theoretical Orientation: CQDs were synthesized using electrochemical redox reactions. Platinum mesh was used for anode and cathode electrodes, and 0.1M NaOH as an electrolyte in a two-compartment cell. For preparation of fluorescent coreshell nanoparticles colloidal synthesis was applied. Findings: Electrochemical carbonization of low molecular weight petrochemical precursors containing carbon, oxygen, and hydrogen resulted in both water-soluble and oil-soluble CQDs of 10-20 nm size. Addition of nitrogen, boron, silicon or sulfur sources to the reaction produced doped CQDs with the fluorescence bands either blue-(N, B or Si) or red-shifted (S) with respect to undoped particles. Synthesized particles were stable for 30 days in API brine at 80�C and have been recovered at 76% in a flow experiments run through Berea sandstone core. Conclusion & Significance: A facile method has been developed for synthesis of large quantities of fluorescent carbon nanoparticles which can be recovered even from low permeable cores. This can open new opportunities for in situ monitoring of reservoir communication and oil production. Recent Publications 1. Zuniga C et al. (2016) Long term high-temperature stability of functionalized graphene oxide nanoplatelets in Arab-D and API brine. ACS Appl. Mater. Interfaces. 8(3):1780-1785. 2. Li H et al. (2012) Carbon nanodots: synthesis, properties and applications. J. Mater. Chem. 22(46):24230-24253. 3. Deng J et al. (2015) Large scale preparation of graphene quantum dots from graphite oxide in pure water via one-step electrochemical tailoring. RSC Adv. 5(38):29704-29707.
A. García Barneto and J. Ariza Carmona are experts on the field of thermal analysis applied to organic materials. They have developed their careers applying thermogravimetric analysis to optimize industrial processes. To this end, they have used autocatalytic models based on Prout-Tompkins equation to deconvolute thermogravimetric curves. In recent times they have applied this approach to the crude oil industry in CEPSA’s refineries. A. González Delgado is a plant manager in La- Rábida CEPSA refinery (Huelva-Spain), being responsible of fuel production.
Statement of the Problem: In order to improve the fuel oil production, engineers need new resources to control the cracking reaction in visbreaking plants. Given the crude oil variability and the chemical complexity of vacuum residue, the optimization of distillates production without compromising fueloil stability is a challenge. As an alternative (or complement) to current situation, thermogravimetric analysis (TGA) provides fast and valuable information about composition of streams entering and leaving visbreaker unit in oil refineries. Methodology & Theoretical Orientation: Over a period of 6 months, the visbreaking unit of La R�bida- CEPSA Refinery (Huelva, Spain) was monitored by analyzing samples of visbreaking feed (VF) and residue (VR) both chemically and thermally. Findings: Thermogravimetric curves can be deconvoluted, allowing thermal-based composition of visbreaking streams to be elucidated by using lumps: four for visbreaking feed and seven for visbreaking residue obtained after thermal cracking. In both cases, some lumps explains volatilization of light substances (viz. naphtha or gasoil) under 350 �C, and some lumps explains cracking of heavy molecules (viz. resins or asphaltenes) at higher temperatures. On this basis can be defined new indices, based on the thermal behavior of samples, that monitor the VF stability and facilitates adjustment of furnace temperature (cracking severity). Conclusion & Significance: Thermogravimetric analysis of visbreaking streams is an alternative to present chemical analysis in order to optimize thermal cracking. Reduces analysis time and provides valuable information to the process engineers in order to maximize middle distillates production and to produce stable fuel oil. Recent Publications 1. Barneto, A.G.; Ariza, J.; Barr�n, (2015) A. Thermogravimetric Monitoring of Crude Oil and its Cuts in an Oil Refinery, Energy and Fuels 29 (3): 2250???2260. 2. Barneto, A.G.; Ariza, J. (2016) Thermogravimetric description of visbreaker streams in an oil refinery. Thermochimica Acta 642:1???9. 3. Joshi, J.B, Pandit, A.B., Kataria, K.L., Kulkarni, R.P., Sawarkar, A.N., Tandon, D., Ram, Y., Kumar, M.M. (2008) Petroleum Residue Upgradation via Visbreaking: A Review, Ind. Eng. Chem. Res., 47: 8960???8988 4. J.G. Speight, Heavy and extra-heavy oil upgrading technologies. (2013) Elsevier. Waltham, MA, USA. 5. E. Alvarez, G. Marroqu�n, F. Trejo, G. Centeno, J. Ancheyta, J. D�az, Pyrolysis kinetics of atmospheric residue and its SARA fractions, (2011) Fuel 90: 3602???3607.