Progress in use of surfactant in nearly static conditions in natural gas hydrate formation

doi:10.1007/s11708-020-0675-2

Front. Energy

2020, Vol. 14

Issue (3) : 463-481 https://doi.org/10.1007/s11708-020-0675-2

REVIEW ARTICLE

Progress in use of surfactant in nearly static conditions in natural gas hydrate formation

Zhen PAN¹, Yi WU¹, Liyan SHANG²(

), Li ZHOU², Zhien ZHANG³

¹. College of Petroleum Engineering, Liaoning Shihua University, Fushun 113001, China
². College of Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
³. William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, OH 43210, USA

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Abstract

Natural gas hydrate is an alternative energy source with a great potential for development. The addition of surfactants has been found to have practical implications on the acceleration of hydrate formation in the industrial sector. In this paper, the mechanisms of different surfactants that have been reported to promote hydrate formation are summarized. Besides, the factors influencing surfactant-promoted hydrate formation, including the type, concentration, and structure of the surfactant, are also described. Moreover, the effects of surfactants on the formation of hydrate in pure water, brine, porous media, and systems containing multiple surfactants are discussed. The synergistic or inhibitory effects of the combinations of these additives are also analyzed. Furthermore, the process of establishing kinetic and thermodynamic models to simulate the factors affecting the formation of hydrate in surfactant-containing solutions is illustrated and summarized.

Keywords gas hydrate kinetic hydrate promoter compounding model surfactant mechanism

Corresponding Author(s): Liyan SHANG

Online First Date: 31 July 2020 Issue Date: 14 September 2020

Cite this article:

Zhen PAN,Yi WU,Liyan SHANG, et al. Progress in use of surfactant in nearly static conditions in natural gas hydrate formation[J]. Front. Energy, 2020, 14(3): 463-481.

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http://journal.hep.com.cn/fie/EN/10.1007/s11708-020-0675-2
http://journal.hep.com.cn/fie/EN/Y2020/V14/I3/463

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Fig.1 Variation of pressure and temperature with time in the formation of hydrate in 3.5°C pure water (adapted with permission from Ref. [²⁷]).

Fig.2 Growth behavior of hydrates on the glass wall as seen from the side (adapted with permission from Ref. [³⁴]).

Fig.3 Micellar system.

Number	Surfactant	Type	Concentration range/ppm	Conclusion	Reference
1	APG	nonionic	0–1600	Among them, at higher concentrations (800–1600 ppm), the formation rate of hydrate in APG solution was very fast, the induction time was shortened to about 15min, and the induction time at 200 ppm in SDBS system was 25–30 min	[⁵⁴]
1	SDBS	anionic	0–2000		[⁵⁴]
2	SDS	anionic	100, 200, 500, 700, 900, 1200	All three can reduce the phase equilibrium point and induction time of the hydrate	[⁷⁷]
	CTAB	cationic	200, 300, 500, 700, 900
	P123	nonionic	100, 300, 500, 900
3	SDS	anionic	300, 500, 1000	SDS effectively accelerated the rate of hydrate formation at three concentrations. LABS increased the rate of hydrate formation at 0.05 wt% and 0.1 wt%, but decreased at 0.03 wt%. In addition, CTAB and ENP promoted the hydrate formation at 0.01 wt%, and weaken at 0.03 and 0.05 wt%	[⁷²]
	LABORATORIES	anionic
	CTAB	cationic
	ENF	nonionic
4	SDS	anionic	300, 500	Compared to pure water, each test can greatly shorten the induction time of hydrate formation in the presence of surfactant. The induction time of the mixture of SDS (ppm) and HTABr (100 ppm) was the smallest	[¹⁰⁶]
	HTABr	cationic	300, 500, 700
	Brij-58	nonionic	300, 500, 700
5	PVP	nonionic	50, 100	PVP showed a dual effect of promoting and inhibiting hydrate nucleation in the test	[⁶⁸]
6	SDS	anionic	80, 125, 1000, 2000, 4000	SDS at 0.1 wt% or above was quite effective for increasing hydrate formation rate and gas conversion rate. STS was less effective to promot hydrate formation	[⁵⁹]
	STS	anionic	7, 35, 100, 400, 600
	SHS	anionic	3, 10, 20, 40, 160
7	LABSA	anionic	50, 100, 1000, 10000	With the addition of LABSA, the rate of hydrate formation increased; low concentrations of ETHOXALATE also increased the rate of hydrate formation, and DAM promoted less than anionic and cationic surfactants	[⁵⁶]
	DAM	cationic
	ETHOXALATE	nonionic
8	Aerosol-OT/AOT	anionic	380	According to the analysis of infrared spectrum, SDS had obvious acceleration effect on hydrate formation, and CPC had no effect on its formation	[⁵³]
	SDS	anionic
	CPC	cationic
9	SDS	anionic		Upon addition of the surfactant, a higher hydrate density was obtained and hydrate formation was accelerated	[⁶]
9	PEG400	cationic			[⁶]
10	SDS	anionic	500, 700, 900, 1100	As the amount of surfactant increased, the rate of hydrate formation increased and the induction time decreased. The effect of anionic SDS on hydrate formation rate was the most significant, and cation HTABr had the greatest influence on induction time	[⁵²]
	HTABr	cationic
	Tritonx-405	nonionic
11	SDS	anionic	1000–4000	When using SDS and SDSN, all reaction times were reduced to less than 40 min. While in SDBS, it took several hours to achieve pressure balance	[⁵⁸]
	SDSN	anionic
	SDBS	anionic
12	SDS	anionic	0, 1000, 2000, 3000	The addition of DTAC had little effect on the formation of methane hydrate. SDS, DAH and DN₂Cl had obvious promoting effects on methane hydrate formation. SDS had a higher hydrate formation rate than the other two,but at 0.1 and 0.2 wt%, DN₂Cl had a better methane uptake than SDS	[⁷⁸]
	DAH	cationic
	DTACl	cationic
	DN₂Cl	nonionic

Tab.1 Summary of different types surfactants on hydrate formation

Fig.4 Process of adsorption of surfactants on surfaces of hydrate particles permission (adapted with from Ref. [⁵¹]).

Fig.5 Molecular structures of three surfactants.

Fig.6 Hydrate formation in (a) APG06, (b) APG0810, and (c) APG1214 aqueous solutions (adapted with permission from Ref. [⁶¹]).

Fig.7 Storage capacity of methane hydrate with and without SDS (adapted with permission from Ref. [⁷¹]).

Tab.2 Summary of hydrate formation in complex systems

Fig.8 Surface tension at the same concentration at 25°C.

Fig.9 Methane consumption during hydrate formation using an SDS/Fe₃O₄ solution for a fixed 4 mmol/L SDS and different Fe₃O₄concentrations, 200, 400, 800, and 1600 mg/L respectively (adap-ted with permission from Ref. [¹⁰⁰]).

Fig.10 Surface tension of mixtures of surfactants SDS and FC-01 at different concentration ratios at 30°C (adapted with permission from Ref. [⁷⁴]).

Fig.11 Induction time after addition of different concentrations of SDS and THF (adapted with permission from Ref. [¹⁰²]).

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