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Frontiers in Energy

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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Zhen PAN
Yi WU
Liyan SHANG
Li ZHOU
Zhien ZHANG
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]
SDBS anionic 0–2000
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]
PEG400 cationic
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]).
Number Compounding Conclusion References
1 SDS+ quartz sand+ NaCl (50, 100, 200 mmol) The combination of porous media and surfactants had a positive effect on hydrate formation kinetics and hydrate formation. When the NaCl concentration was 50 mmol, the methane consumption was higher than that of pure water [11]
2 T40, T40/T80 (1:1), T40/T80 (4:1) Surfactant T40 had a more pronounced effect in promoting hydrate nucleation and shortening induction time compared to the compound system [37]
3 SDS (0.01, 0.05, 0.1, 0.15 wt%) + 3 mol% THF The addition of THF further increased the rate of hydrate formation, shortened the induction time, and the gas consumption could be more than twice [102]
4 SDS (0.005, 0.05 wt%) + 5 mol% THF The solution system after the addition of THF had a faster nucleation rate and a higher gas storage capacity [103]
5 propanone+ SDS The rate of hydrate formation was not significantly affected when the acetone concentration was less than 0.03 mol, but the rate of formation of hydrate was increased at high concentrations [105]
6 THF, SDS+ THF, SDBS+ THF The addition of an anionic surfactant increased the rate of hydrate formation. In contrast, the rate of formation of hydrates in THF+ SDBS was much better than that of THF+ SDS [104]
7 TBAB+ SDS The addition of 0.15 wt% SDS to the 20 wt% TBAB system increased the gas consumption rate to 177% [107]
8 TBAB+ SDS+ silica sand The amount of methane absorbed in the TBAB+ SDS system was higher than in other systems, indicating that the two surfactants produced a synergistic effect. In addition, it had good hydrate kinetics in porous media [108]
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]).
n Oxygen-oxygen logarithm of water molecules
a Activity
ΔH Enthalpy of formation of a hydrate/J
T Hydrate formation temperature in the presence of an inhibitor/K
T0 Hydrate formation temperature of pure water/K
R Universal gas constant
x Mole fraction
Greek letters
ϕ Twist angle between the farthest O-H vectors of the two water molecules
Subscripts
w Water
a Acetone
  
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