A Theoretical Investigation of the Structure and Reactivity of the Molecular Constituents of Oil Sand and Oil Shale

Technical Report · Mon Nov 28 00:00:00 EST 2016

DOI:https://doi.org/10.2172/1333568· OSTI ID:1333568

Parish, Carol A. ^[1]

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1. Univ. of Richmond, VA (United States)

We used a variety of small organic models of asphaltenes to investigate the molecular mechanism for the high temperature decomposition that would take place as part of the oil refinery process. We determined that the decomposition is initiated via four different types of hydrogen migration reactions. According to the energetics of the reactions, the dominant 1,2-H shift mechanism involves two competitive product channels, namely, C₂H₂ + CH₂CS and CS + CH₃CCH. The minor channels include the formation of CS + CH₂CCH₂, H₂S + C₄H₂, HCS + CH₂CCH, CS + CH₂CHCH, H + C₄H₃S, and HS + C₄H₃. We also investigated the alkyl substitution effect by exploring the decomposition pathways of models with alkyl arms. The energetics of such systems were very similar to that for unsubstituted model compounds, which suggests that asphaltene alkylation may not play a significant role in the decomposition of asphaltene compounds. This work was published in the Journal of Physical Chemistry A 2011, 115, 2882-2891. A MECHANISTIC STUDY OF THE 2-THIENYLMETHYL + HO2 RADICAL RECOMBINATION REACTION Radicals are molecules which contain single electrons. They are very reactive. Radical recombination reactions are important in the combustion of fuel oils. Shale oil contains radicals. We used quantum mechanics to explore the reactivity of shale oil model radical compounds. Seventeen product channels corresponding to either addition/elimination or direct hydrogen abstraction were characterized. Direct hydrogen abstraction proceeds via a weakly bonded complex, which leads to 2-methylthiophene, 2-methylene-2,3-dihydrothiophene or 2-methylene-2,5-dihydrothiophene depending upon the 2-thienylmethyl radical reaction site. The addition pathway for the two radical reactants is barrierless with the formation of three adducts, as distinguished by HO₂ reaction at three different sites on the 2-thienylmethyl radical. The addition is exothermic by 37 ~ 55 kcal mol-1 relative to the entrance channel. These excess energies are available to promote further decomposition or rearrangement of the adducts that lead to nascent products such as H, OH, H₂O and CH₂O. The reaction surfaces are characterized by relatively low barriers (most are lower than 10 kcal mol-1). Based upon a careful analysis of the overall barrier heights and reaction exothermicities, the formation of O2, OH and H2O is likely to be an important pathway in the radical recombination reactions of 2-thienylmethyl + HO₂. This work was published in the Journal of Physical Chemistry A, 2011, 115, 14546-14557. REACTION OF THIOPHENE AND METHYLTHIOPHENE WITH SINGLET AND TRIPLET MOLECULAR OXYGEN Mechanisms for the reaction of thiophene and 2-methylthiophene with molecular oxygen on both the triplet and singlet potential energy surfaces (PESs) were investigated using ab initio methods. Thiophene and 2-methylthiophene where shown to react with O₂ via two types of mechanisms; namely, direct hydrogen abstraction and addition/elimination. The barriers for reaction with triplet oxygen are all significantly large (i.e., > 30 kcal mol-1), which indicates that the direct oxidation of thiophene by ground state oxygen might be important only in high temperature processes. Reaction of thiophene with singlet oxygen via a 2+4 cycloaddition leading to endoperoxides is the most favorable channel. Moreover, it was found that alkylation of the thiophene ring (i.e., methyl-substituted thiophene) is capable of lowering the barrier height for the addition pathway. The implication of the current theoretical results may shed new light on the initiation mechanisms for combustion of asphaltenes. This work was published in the Journal of Physical Chemistry A, 2012 116, 4934-4946. JAHN-TELLER STABILIZATION IN POSS CATIONS We have a long standing interest in polyoligomeric silsesquioxane (POSS) molecules.^1-2 These molecules have recently been used as advanced surface coatings for photovoltaic devices and have potential as molecular-based energy storage devices as well as magnetically controllable liquid marbles.^3-5 We have been investigating the small molecule encapsulation properties of POSS and discovered some interesting symmetry breaking processes that need to be better understood in order to use POSS in advanced materials. We have investigated this symmetry breaking mechanism in POSS monocations Si8O12(C(CH3)3)8+ and Si8O12Cl8+, using density functional theory (DFT) and group theory. Under Oh symmetry, these ions possess 2T2g and 2Eg electronic states, respectively, and undergo different symmetry breaking mechanisms. The ground states of Si₈O₁₂(C(CH₃)₃)₈⁺ and Si₈O₁₂Cl₈⁺ belong to the C_3v and D_4h point groups and are characterized by Jahn-Teller stabilization energies of 3959 and 1328 cm-1, respectively, at the B3LYP/def2-SVP level of theory. The symmetry distortion mechanism in Si₈O₁₂Cl₈⁺ is Jahn-Teller type, whereas in Si₈O₁₂(C(CH₃)₃)₈⁺ the distortion is a combination of both Jahn-Teller and pseudo-Jahn-Teller effects. The distortion force acting in Si₈O₁₂(C(CH₃)₃)₈⁺ is mainly localized on one Si-(tert-butyl) group while in Si₈O₁₂Cl₈⁺ it is distributed over the oxygen atoms. The main distortion forces acting on the Si8O12 core arise from the coupling between the electronic state and the vibrational modes; identified as 9t_2g+1e_g+3a_2u for the Si₈O₁₂(C(CH₃)₃)₈⁺ and 1e_g+2e_g for Si₈O₁₂Cl₈⁺. This work was published in the Journal of Physical Chemistry A, 2015, 119, 4237-4243.

• Research Organization: Univ. of Richmond, VA (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: SC0001093
• OSTI ID: 1333568
• Report Number(s): Final-DOE-UR-1093
• Country of Publication: United States
• Language: English

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04 OIL SHALES AND TAR SANDS