Kinetics and Abnormal Inhibition of THF on Ethylene Hydrate Formation from Ice Powder Based on Conversion Rate†

doi:10.7503/cjcu20180234

Abstract

Abstract:

The conversion rate of ice powder(α), as a key parameter on evaluation of hydrate formation from ice-gas interface, was calculated by using compressibility non-ideal gas equation. And the Avrami equation and the Arrhenius equation were combined to investigate the kinetic information and influence rule of temperature, pressure, and tetrahydrofuran(THF) on the synthesis of ethylene hydrate from ice. As a result, there is no induction period during the formation of ethylene hydrate from ice. And the ethylene hydrate is rapidly nucleated on the ice surface and grows in the one-dimensional direction with the same rate. The activation energy(E_a) of ethylene hydrate from ice powder is 21.28 kJ/mol at 260.05—269.75 K, which is much lower than that in aqueous phase. The final α is 19.20% under the initial ethylene pressure of 4.90 MPa and 269.75 K. The α rises with the pressure from 1.98 MPa to 4.90 MPa and temperature from 250.46 K to 269.75 K. And THF can reduce α and conversion efficiency of α, which can identify that THF has abnormal inhibition on the formation of ethylene hydrate from ice by molecular size effect.

Key words: Ice powder, Ethylene hydrate, Kinetics, Avrami and Arrhenius equation, Tetrahydrofuran(THF)

CLC Number:

O647.32

TrendMD:

SHI Weiguang,QING Hongxia,ZHANG Shangshang,LU Xiaoyi,WANG Xiaofeng,LI Benxian,XU Xiaohu,LIU Weiguo,WANG Jun,DONG Zhaohui. Kinetics and Abnormal Inhibition of THF on Ethylene Hydrate Formation from Ice Powder Based on Conversion Rate^†[J]. Chem. J. Chinese Universities, 2018, 39(9): 1968.

Figures/Tables 10

Fig.1 Schematic of hydrate experimental system

Table 1 Compressibility factors of general gas

T₁/K	p₁/MPa	$Z 1 [28]$	T₂/K	p₂/MPa	$Z 2 [28]$
269.75	4.90	0.47	268.92	3.86	0.57
269.75	3.36	0.65	269.12	2.85	0.72
269.75	1.98	0.83	269.12	1.70	0.85

Table 1 Compressibility factors of general gas

T₁/K	p₁/MPa	$Z 1 [28]$	T₂/K	p₂/MPa	$Z 2 [28]$
269.75	4.90	0.47	268.92	3.86	0.57
269.75	3.36	0.65	269.12	2.85	0.72
269.75	1.98	0.83	269.12	1.70	0.85

Fig.2 Pressure vs. time during the formation of ethylene hydrate from ice powder

Fig.3 Schematic of hydrate formation

Fig.4 Conversion rate of ice powder(A) and Avrami plots(B) of ethylene hydrate at 250.46 K(a), 260.05 K(b), 263.11 K(c), 266.32 K(d) and 269.75 K(e)

Table 2 Avrami constants for different temperatures

Temperature/K	n	Dimensionality of crystal growth	lnk_a
269.75	0.075	1D	-25.38
266.32	0.077	1D	-25.52
263.11	0.080	1D	-25.63
260.05	0.083	1D	-25.74
250.46	0.053	1D	-42.53

Fig.5 Arrhenius plot of ethylene hydrate at different temperatures

Fig.6 Pressure vs. time(A), conversion rate(B), conversion efficiency(C) of ethylene hydrate under different initial pressures

Fig.7 Temperature vs. time during the formation of ethylene hydrate with different dosage of THF

Fig.8 Pressure vs. time(A), conversion rate(B), conversion efficiency(C) of ethylene hydrate with different dosage of THF

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