Study on the synergistic effect of NaOH and CuSO4 in aquathermolysis upgrading

Zhou, Yantao; Zhao, Qiuyang; Yan, Miao; Wang, Xuetao; Zhang, Yanlong; Wang, Yechun; Guo, Liejin

doi:10.1016/j.fuproc.2023.107715

Cited by 7 publications

(4 citation statements)

References 38 publications

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“…Several alkaline homogeneous additives such as NaOH, KOH, Ca(OH) 2 , K 2 CO 3 , NaHCO 3 , and Na 2 CO 3 have provided an increase in the efficiency of gasification processes and upgrading of heavy crude and vegetable oils since they can dissolve in the hydrothermal medium and promote hydrogen yield by accelerating the water gas shift reaction by CO 2 absorption. − The kinetic changes for the asphaltene transformation under the SCW environment in the presence of NaOH were analyzed using the results obtained for the reconciliation data procedure at 450 °C and the estimation of the kinetic parameters using the selected reaction scheme (Figure ). Table shows the kinetic coefficients for asphaltene conversion in the absence and presence of NaOH at 450 °C, where the AAE value of 6.73% indicates adequate agreement of the model predictions with the experimental data.…”

Section: Resultsmentioning

confidence: 99%

Kinetic Analysis of Asphaltene Conversion under Supercritical Water Conditions

Tirado,

Félix,

Varfolomeev

et al. 2024

Ind. Eng. Chem. Res.

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Kinetic studies of chemical compounds in crude oil are essential to provide a better understanding of the reaction mechanisms occurring under heavy crude oil upgrading conditions. This study analyzes the reaction kinetics of asphaltenes, the most complex fraction of crude oil, under supercritical water (SCW) conditions for the upgrading of heavy crude oil. Experimental data reported in the literature and a proper reaction scheme were analyzed to develop kinetic models capable of predicting the reactive behavior of asphaltenes and their reaction products. The results showed that asphaltenes are mainly converted to coke, while the selectivity toward maltene and gas compounds varies considerably concerning the reaction temperature. Additionally, produced maltenes undergo cracking reactions to produce gases or condensation/polyaddition, generating asphaltenes. Furthermore, the effect of NaOH on the diverse reaction rates during asphaltene conversion was analyzed. The predictions of the developed models show adequate agreement with the experimental data, corroborating that the proposed reaction scheme correctly represents the asphaltene transformation and its reaction products under SCW conditions.

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Section: Resultsmentioning

confidence: 99%

Kinetic Analysis of Asphaltene Conversion under Supercritical Water Conditions

Tirado,

Félix,

Varfolomeev

et al. 2024

Ind. Eng. Chem. Res.

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“…Although some M−OH have been reported for hydrothermal processes, all of them are based on nontransition metals, such as Na, K, and Ca. 31,41,42 Previous reports have suggested that the catalysts based on transition metals show better catalysis. 24−31,35−38 However, to the best of our knowledge, there has been no report on the catalytic SCWU of heavy oil using transition-metal hydroxides.…”

Section: Introductionmentioning

confidence: 99%

“…Although MO n exhibits good catalysis performance, the cost of producing MO n nanoparticles is significantly high. Moreover, the nanoparticles agglomerate easily. The second type is the water-soluble inorganic metal salts (M-IAc), such as Zn(NO 3 ) 2 , CuSO 4 , and FeSO 4 . − They are usually prepared as an aqueous solution for catalytic hydrothermal upgrading, by which the M-IAc can be dispersed homogeneously. Moreover, the M-IAc can be thermally hydrolyzed to produce the corresponding MO n and inorganic acid (H-IAc) under hydrothermal conditions normalt hermal hydrolysis : normalM ‐ IAc + normalH 2 O → MO n + H ‐ IAc It should be pointed out that M-IAc is the main precursor reagent to synthesize the aforementioned MO n nanoparticles via the hydrothermal method .…”

Section: Introductionmentioning

confidence: 99%

“…The second type is the water-soluble inorganic metal salts (M-IAc), such as Zn(NO 3 ) 2 , CuSO 4 , and FeSO 4 . − They are usually prepared as an aqueous solution for catalytic hydrothermal upgrading, by which the M-IAc can be dispersed homogeneously. Moreover, the M-IAc can be thermally hydrolyzed to produce the corresponding MO n and inorganic acid (H-IAc) under hydrothermal conditions normalt hermal hydrolysis : normalM ‐ IAc + normalH 2 O → MO n + H ‐ IAc …”

Section: Introductionmentioning

confidence: 99%

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Metal Hydroxide-Catalyzed Heavy Oil Upgrading in Supercritical Water: Deuterium Tracing Study

Chen,

et al. 2024

Energy Fuels

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Conversion of heavy oil is urgent as most of the explored fossil oil reserves and renewable raw biodiesel can be categorized as heavy oil. Supercritical water upgrading (SCWU) is a green and promising technology for heavy oil conversion, but the hydrogen-donating capacity of pure water is inadequate. This study adopts transition-metal hydroxide (M−OH) to enhance the in situ hydrogen-donating capacity of water for the first time. Both M− OH and the corresponding metal oxide nanoparticle (MO n ) of one post-transition metal (Al) and five transition metals (Cr, Cu, Fe, Ni, Zn) are tested. The SCWU conditions are selected as 425 °C, 60 min, water-to-oil ratio of 4:1, catalyst-to-oil ratio of 1:10, and water density of 308 kg m −3 . Deuterium oxide (D 2 O) instead of H 2 O is used as the reaction medium for a deuterium tracing study. Results indicate that the different metal-based MO n nanoparticles display various effects on heavy hydrocarbon cracking, gasification, coke suppression, and D addition reactions. The overall performance is found to be on the order of NiO > Cr 2 O 3 > Fe 2 O 3 > CuO > Al 2 O 3 > ZnO. Compared to MO n , M−OH can generally improve the oil yield and H/C ratio and reduce the coke yield simultaneously. The mechanism analysis suggests that the M−OH decomposition behavior under hydrothermal conditions is the primary cause by which MO n and lattice H 2 O are generated in the oil-rich phase. The lattice H 2 O can not only take part in SCWU reactions but also suppress coke formation. In conclusion, M−OH is a promising catalyst as it combines the good dispersibility and catalytic activity of MO n nanoparticles and the low cost of water-soluble inorganic metal salts (M-IAc) but does not result in any corrosive species, such as inorganic acid from M-IAc.

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