Effects of deep eutectic solvents on H₂SO₄‐catalyzed alkylation: Combining experiment and molecular dynamics simulation

Abstract

To enhance the catalytic performance of H2SO4‐catalyzed alkylation, various catalytic additives have drawn considerable attentions. Herein, the effects of deep eutectic solvent (DES) additives on catalytic performance and the interfacial properties of H2SO4 alkylation were systematically investigated using experimental methods and molecular dynamics (MD) simulation. Experimental results indicate that DESs with the optimal concentration about 1.0 wt% can efficiently improve C8 selectivity and research octane number of alkylate, especially at low temperature, but contribute less to the lifetime of H2SO4. MD results reveal that the phenyl molecules of DESs additives play a major role in enhancing interfacial properties of H2SO4 alkylation, including enlargement of interfacial thickness, promotion of isobutane relative solubility and diffusion to butene, which is probably the main reason for the better quality of alkylate. This work gives a good guideline for the design of novel DESs for H2SO4 alkylation.

Enhanced catalytic performance of H2SO4‐catalyzed C4 alkylation by formyl functional [N1,1,1,1][C10SO4] additive

“…In the used H 2 SO 4 ‐catalyzed alkylation, the RON and C 8 components approach a plateau basically at 15 min, which is the same as the fresh concentrated H 2 SO 4 ‐catalyzed alkylation 21 . However, with the addition of formyl functional [N 1,1,1,1 ][C 10 SO 4 ], the reaction equilibrium time is reduced to 10 min at 281.15 K, 10 min at 285.15 K, and 5 min at 289.15 K, respectively, which demonstrates that formyl functional [N 1,1,1,1 ][C 10 SO 4 ] additive has a positive effect on accelerating the reaction rate.…”

“…Sulfurous acid, decyl pentyl ester 0.17 In the used H 2 SO 4 -catalyzed alkylation, the RON and C 8 components approach a plateau basically at 15 min, which is the same as the fresh concentrated H 2 SO 4 -catalyzed alkylation. 21 However, with the addition of formyl functional [N To fit the experimental data and estimate rate constants in Equations S1-S12, the nonlinear least-squares fitting methods were used with the following function,…”

“…The effects of ILs and DESs additives on the H 2 SO 4catalyzed C4 alkylation were investigated in details by Tang et al, 13 followed by Zhang et al, [14][15][16] Liu et al, 17 and our groups. [18][19][20][21] It has been well proven that the ILs and DESs additives can significantly intensify the interfacial properties and catalytic performance of H 2 SO 4 -catalyzed C4 alkylation. However, DESs additives, such as choline chlorides-phenol and choline chlorides-benzoic acid, contain halogen elements that can accelerate equipment corrosion, and ILs additives still suffer from limitations in industrial application owing to the high cost of raw materials and complicated preparation process.…”

“…Various additives including surfactants, deep eutectic solvents (DESs), and ILs have been successfully developed to enhance the catalytic performance of H 2 SO 4 ‐catalyzed C4 alkylation. The effects of ILs and DESs additives on the H 2 SO 4 ‐catalyzed C4 alkylation were investigated in details by Tang et al, 13 followed by Zhang et al, 14–16 Liu et al, 17 and our groups 18–21 . It has been well proven that the ILs and DESs additives can significantly intensify the interfacial properties and catalytic performance of H 2 SO 4 ‐catalyzed C4 alkylation.…”

Assessing Industrial-Scale H2SO4-Catalyzed C4 Alkylation Enhanced by [N1,1,1,1][C10SO4] Additives Based on a Complex Kinetic Model

“…After the reaction, the samples were analyzed by gas chromatography (GC). The details of the analysis of the samples are displayed in our previous work. , …”