Deep Insights into Heavy Oil Upgrading Using Supercritical Water by a Comprehensive Analysis of GC, GC-MS, NMR, and SEM-EDX with the Aid of EPR as a Complementary Technical Analysis

Richard Djimasbe; Mikhail A Varfolomeev; Ameen A Al-Muntaser; Chengdong Yuan; Muneer A Suwaid; Dmitriy A Feoktistov; Ilfat Z Rakhmatullin; Aleksei A Milovankin; Fadis Murzakhanov; Vladimir Morozov; Marat Gafurov; Abdolreza Farhadian; Rustam R Davletshin

doi:10.1021/acsomega.0c03974

Deep Insights into Heavy Oil Upgrading Using Supercritical Water by a Comprehensive Analysis of GC, GC-MS, NMR, and SEM-EDX with the Aid of EPR as a Complementary Technical Analysis

ACS Omega. 2020 Dec 28;6(1):135-147. doi: 10.1021/acsomega.0c03974. eCollection 2021 Jan 12.

Authors

Richard Djimasbe^{1

2}, Mikhail A Varfolomeev^{1

2}, Ameen A Al-Muntaser^{1

2}, Chengdong Yuan^{1

2}, Muneer A Suwaid^{1

2}, Dmitriy A Feoktistov³, Ilfat Z Rakhmatullin⁴, Aleksei A Milovankin³, Fadis Murzakhanov^{2

4}, Vladimir Morozov⁵, Marat Gafurov^{2

4}, Abdolreza Farhadian^{1

2}, Rustam R Davletshin⁶

Affiliations

¹ Department of Petroleum Engineering, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia.
² Department of Physical Chemistry, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia.
³ Institute of Geology and Petroleum Technologies, Kazan Federal University, Kremlevskaya 4/5, Kazan 420008, Russia.
⁴ Institute of Physics, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia.
⁵ Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzova 8, Kazan 420088, Russia.
⁶ Alexander Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia.

Abstract

Upgrading of heavy oil in supercritical water (SCW) was analyzed by a comprehensive analysis of GC, GC-MS, NMR, and SEM-EDX with the aid of electron paramagnetic resonance (EPR) as a complementary technical analysis. The significant changes in the physical properties and chemical compositions reveal the effectiveness of heavy oil upgrading by SCW. Especially, changes of intensities of conventional EPR signals from free radicals (FRs) and paramagnetic vanadyl complexes (VO²⁺) with SCW treatment were noticed, and they were explained, respectively, to understand sulfur removal mechanism (by FR intensity and environment destruction) and metal removal mechanism (by VO²⁺ complexes' transformation). For the first time, it was shown that electronic relaxation times extracted from the pulsed EPR measurements can serve as sensitive parameters of SCW treatment. The results confirm that EPR can be used as a complementary tool for analyzing heavy oil upgrading in SCW, even for the online monitoring of oilfield upgrading.