<p>Alkaline desulfurization of unstable light virgin naphtha is a key industrial process for removing sulfur compounds prior to further fuel utilization, ensuring compliance with increasingly stringent sulfur regulations and minimizing sulfur-related emissions. Despite its industrial relevance, kinetic information for this process under real operating conditions remains limited. This study uses industrial plant data to identify reaction kinetics under real operating conditions. Two data-driven kinetic identification methods were evaluated using 41 industrial trials: global vector field reconstruction and direct derivative modeling. The direct derivative approach successfully reproduced concentration trajectories and time derivatives in 32 trials (78%), achieving an average coefficient of determination of <InlineEquation ID="IEq1"> <EquationSource Format="TEX">$R^2 = 0.9750 \pm 0.0349$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msup> <mi>R</mi> <mn>2</mn> </msup> <mo>=</mo> <mn>0.9750</mn> <mo>±</mo> <mn>0.0349</mn> </mrow> </math></EquationSource> </InlineEquation>, while global reconstruction showed lower robustness and higher variability. Phase-space dimensionality analysis indicated predominantly three-dimensional dynamics, consistent with the coupled behavior of NaOH, <InlineEquation ID="IEq2"> <EquationSource Format="TEX">$\hbox {H}_{2}\hbox {S}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msub> <mtext>H</mtext> <mn>2</mn> </msub> <mtext>S</mtext> </mrow> </math></EquationSource> </InlineEquation>, and mercaptans. Spectral analysis confirmed monotonic, irreversible kinetics under plant conditions. The recovered rate expressions contain a dominant positive quadratic term, supporting an autocatalytic inhibition reaction mechanism. This study demonstrates that kinetic expression can be obtained directly from industrial operational data without laboratory experiments or additional instrumentation. The proposed methodology relies solely on routinely collected operational data and is readily applicable at industrial scale. The resulting kinetic model provides a practical tool for estimating sulfur removal, supporting process analysis, design, and optimization of industrial unstable naphtha desulfurization units.</p>

Recovering reaction kinetics from plant data: application to the alkaline desulfurization of unstable naphtha

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发表日期：

2026年2月9日

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Roxana Cortés Martínez,
Alejandro Valdés López,
Alejandro Alonzo García,
E. C. Herrera-Hernández

摘要

Alkaline desulfurization of unstable light virgin naphtha is a key industrial process for removing sulfur compounds prior to further fuel utilization, ensuring compliance with increasingly stringent sulfur regulations and minimizing sulfur-related emissions. Despite its industrial relevance, kinetic information for this process under real operating conditions remains limited. This study uses industrial plant data to identify reaction kinetics under real operating conditions. Two data-driven kinetic identification methods were evaluated using 41 industrial trials: global vector field reconstruction and direct derivative modeling. The direct derivative approach successfully reproduced concentration trajectories and time derivatives in 32 trials (78%), achieving an average coefficient of determination of $R^2 = 0.9750 \pm 0.0349$ $R^{2} = 0.9750 \pm 0.0349$ , while global reconstruction showed lower robustness and higher variability. Phase-space dimensionality analysis indicated predominantly three-dimensional dynamics, consistent with the coupled behavior of NaOH, $\hbox {H}_{2}\hbox {S}$ $H_{2} S$ , and mercaptans. Spectral analysis confirmed monotonic, irreversible kinetics under plant conditions. The recovered rate expressions contain a dominant positive quadratic term, supporting an autocatalytic inhibition reaction mechanism. This study demonstrates that kinetic expression can be obtained directly from industrial operational data without laboratory experiments or additional instrumentation. The proposed methodology relies solely on routinely collected operational data and is readily applicable at industrial scale. The resulting kinetic model provides a practical tool for estimating sulfur removal, supporting process analysis, design, and optimization of industrial unstable naphtha desulfurization units.