Insight into thermal dissociation of tri‐n‐octylamine hydrochloride: The key to realizing CO₂ mineralization with waste calcium/magnesium chloride liquids

Abstract

A thermal dissociation process (ideally, 100% atom utilization) to regenerate the amine extractant and to produce gaseous HCl which is the key to realizing the CO2 mineralization with metal chloride waste liquids was investigated. Solvent effects on the thermal dissociation of tri‐n‐octylamine hydrochloride (TOAHCl) were predicted to be prominent via analyzing structure parameters, charge distribution, solvation free energy, apparent basicity, and N‐H frequency with the help of molecular simulation and experiments. Inert solvents with low polarity such as decalin, dodecane were favorable in thermal dissociation experiments. In particular, decalin enhanced the dissociation most effectively which is in agreement with the prediction. In dilute solutions, the thermal dissociation kinetics was shown to be first order. The apparent reaction rate (3.0 × 10−4−1.5 × 10−2 min−1) and activation energy (58.219‐121.827 kJ/mol) differ a lot at 180‐190°C in various solvents, confirming a strong solvent effect. A two‐stage reaction scheme in dilute solutions has been proposed from the experimental study. The overall process is entropically driven, with the removal of HCl into gas phase from the solvated state. The work could offer a fundamental direction for the further actual process.

Effect of solvent on the thermal dissociation of TOAHCl through DFT and MD

“…TOA (≥95%) was purchased from Shanghai Macklin Biochemical Co., Ltd. Decalin (GR, ≥99.5%), tetralin (CP, ≥98.0%), n-octanol (AR, ≥99.0%), hydrochloric acid (AR) was purchased from Sinopharm Chemical Reagent Co., Ltd. n-undecane (GR, ≥99%), n-dodecane (GR, ≥99%), npentadecane (GR, ≥99%), n-hexadecane (GR, ≥99%), was purchased from Shanghai Titan Scientific Co.,Ltd. The thermal dissociation experiments refered to Dong [6] .…”

Applied techniques for residual oil recovery from source rocks: A review of current challenges and possible developments

“…9.08 1.60 1.32 5.20-25. 30 Reinhardt et al [57] Chlorobenzene 5.50 1.60 1.11 0.05 Bogacki and Zawadzki [58] Diethyl ether 4.40 1.20 0.71 6.90 Douglas et al [50] Dibutyl ether 3.10 1.20 0.77 0.30 Samec et al [59] Dimethyl ether 3.10 1.30 0.78 Miscible Dong et al [60] Ethyl acetate 6.40 1.80 0.90 7. 94 Li et al [61] Methyl isobutyl ketone [62] F I G U R E 3 Schematic diagram of nanoparticles fracturing chemicals penetration within shale nanopores and cavities However, the particles can be deformed and enter deep into the nanopores within the shale formation.…”

“…Hexane 1.98 0 0.66 0.01 DiStefano et al [49] Benzene 2.28 0 0.88 0.08 Douglas et al [50] Acetone 21.10 2.91 0.7845 Miscible Wang et al [51] Cyclohexane 2.02 0 0.78 0.005 Ngnie et al [52] Toluene 2.33 0.31 0.87 0.05 Abourriche et al [53] m-Xylene 2.40 0.40 0.86 0.01 Olaguer et al [54] Chloroform 4.81 1.04 1.49 0.81 Akondi et al [55] Carbon tetrachloride 2.20 0 1.58 0.08 Zhao et al [56] Methylene chloride (DCM) [57] Chlorobenzene 5.50 1.60 1.11 0.05 Bogacki and Zawadzki [58] Diethyl ether 4.40 1.20 0.71 6.90 Douglas et al [50] Dibutyl ether 3.10 1.20 0.77 0.30 Samec et al [59] Dimethyl ether 3.10 1.30 0.78 Miscible Dong et al [60] Ethyl acetate 6.40 1.80 0.90 7. 94 Li et al [61] Methyl isobutyl ketone 13.10 2.69 0.80 1.70 Samec et al [59] Cyclohexane 18.2 2.8 0.95 2.3 Dong et al [62] F I G U R E 3 Schematic diagram of nanoparticles fracturing chemicals penetration within shale nanopores and cavities However, the particles can be deformed and enter deep into the nanopores within the shale formation.…”

Selecting solvents for intensification of thermal dissociation of tri-n-octylamine hydrochloride by calculating infrared spectra from ab initio molecular dynamics

“…It is known that solvents have substantial effect on the thermal dissociation of tri-n-octylamine hydrochloride (TOAHCl) [9]. As the dissociation reaction involves breaking the N-H bond, the N-H stretching vibrations will be an important indication of TOAHCl's stability, and a sensitive marker of the chemical environment.…”