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Journal of Chinese Society for Corrosion and protection  2023, Vol. 43 Issue (6): 1203-1215    DOI: 10.11902/1005.4537.2022.410
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Research Progress of Detection Techniques for Permeated Hydrogen
ZHOU Xin1, WU Dakang2, CHENG Xu2, HU Junying1, ZHONG Xiankang1,3()
1.School of Oil and Natural Gas Engineering, Southwest Petroleum University, Chengdu 610500, China
2.No. 12 Oil Production Plant of Changqing Oilfield, Xi'an 710200, China
3.State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
Cite this article: 

ZHOU Xin, WU Dakang, CHENG Xu, HU Junying, ZHONG Xiankang. Research Progress of Detection Techniques for Permeated Hydrogen. Journal of Chinese Society for Corrosion and protection, 2023, 43(6): 1203-1215.

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Abstract  

In order to achieve the goals of the “peak carbon dioxide emission and carbon neutrality”, it is essential to develop hydrogen energy. During the production, transportation, storage and use of hydrogen, hydrogen permeation is easy to occur and causes hydrogen damage to metal materials, which not only shortens the service life of pipelines and equipment, but also brings serious potential safety hazards. So it is of great significance to promote the development of permeated hydrogen detection techniques. Permeated hydrogen testing technology can be divided into indoor- and field-permeated hydrogen testing techniques. The indoor permeated hydrogen testing techniques include current method, hot/melt extraction, thermal desorption spectroscopy (TDS), hydrogen micro-contact printing (HMP), scanning Kelvin probe force microscopy (SKPFM), secondary ion mass spectroscopy (SIMS), atom probe tomography (APT) and neutron radiography (NRG). The field permeated hydrogen testing techniques include hydrogenochromic method, hydrogen flux method, hydrogen probe method, hydrogen sensor, as well as field Kelvin probe (FKP) technique. For the indoor testing, the principles and characteristics of several detection techniques were summarized and applicable scope was also introduced. The current method, hot/melt extraction and TDS are used to measure the average hydrogen concentration in materials, but none of the above methods have the ability of spatial resolution. The silver particles produced by the substitution reaction between Ag+ and H by HMP reflect the distribution and diffusion path of hydrogen, but it is not certain whether Fe participates in that. By continuously detecting the potential of a certain position, SKPFM can reveal the hydrogen enrichment and the dynamic process of diffusion in a specific position. However, when current/potential is applied on the sample surface, it will disturb the test results. Both SIMS and APT technology rely on mass spectrometry, and have spatial resolution but their measuring chamber need to be filled with deuterium to eliminate the influence of background hydrogen. NRG can judge the concentration and distribution of hydrogen by detecting the hydrogen intensity and bright area, but its spatial resolution can only reach micron level. For the field testing, the parameters of several testing equipment provided on the market are investigated in this article, while the principle, application scope, advantages and disadvantages of each method are also summarized. Finally, some suggestions are put forward for the future development of hydrogen permeation detection methods.

Key words:  permeated hydrogen      detection      hydrogen energy      hydrogen-containing pipeline      hydrogen-containing equipment     
Received:  26 December 2022      32134.14.1005.4537.2022.410
ZTFLH:  TG172  
Fund: National Natural Science Foundation of China(52171080);Sichuan Science and Technology Plan Project
Corresponding Authors:  ZHONG Xiankang, E-mail: zhongxk@yeah.net

URL: 

https://www.jcscp.org/EN/10.11902/1005.4537.2022.410     OR     https://www.jcscp.org/EN/Y2023/V43/I6/1203

Trap typeBlinding energy kJ·mol-1Reference
Vacancy30-60[22], [23]
Microvoid40[24]
Dislocation20-30[25], [26]
Strain field12-27[27], [28], [29]
GB9-49[27], [30], [31]
Prior austenite47[32]
Austenite-ferrite44[33]
Iron oxide interface43-62[24]
Table 1  Common hydrogen traps and their trapping energies
NameSensitivity 10-12 L·cm-2·s-1Response time / sRange of hydrogen flux 10-12 L·cm-2·s-1
Hydrosteel 6000±1<500-15000
Hydrosteel 65002901-20000
Hydrosteel 70001<1801-2000
Table 2  Parameter of hydrogen flux method
NameTypeMaximum pressure / MPaRange MPaLength m
HY 4000Intrusive13.790-0.280.089
HY 7000Intrusive24.820-0.410.076
HY 7001Non-intrusive24.82
Table 3  Parameter of hydrogen probe method
NameSensitivityRange mg·kg-1Response time / sTemperature range / ℃Humidity range / RH%
CAT16

>0.012 v%

methane

0-40000<10-40-+5015-90
CAT25

>0.012 v%

methane

0-40000<10-40-+5015-90
4-LEL-4.25V

0.032±0.01 v%

methane

0-40000<20-20-+5015-90
4-LEL-2.3V

0.023±0.07 v%

methane

0-40000<20-20-+5015-90
TGS6812-D000.008-0.016 v in 4000 mg·kg-10-40000-10-+700-95
CGM6812-B000-14000≤30-60-+7020-95
Table 4  Parameter of catalytic hydrogen sensor
NameSensitivity μA·mg-1·kgRange / mg·kg-1Response time / sTemperature range / ℃Humidity range RH%Service life a
4-H2-10000.02±0.010-1000≤70-20-+5015-902
4-H2-400000.007±0.0020-40000≤60-20-+5015-902

(0-20000)

PPM H2

0.003±0.0020-20000

T50:<10

T90:<30

>5

(0-1000)

PPM H2

ME3-H2

ME4-H2

0.008±0.003

0.01±0.005

0.03±0.01

0-1000

0-1000

0-1000

T50:<10

T90:<30

T90:≤90

T90:≤30

-20-+50

-20-+50

15-90

15-90

>5

2

2

ME2-H20.002±0.0010-30000T90:<30-20-+5015-903
Table 5  Parameter of electrical current hydrogen sensor
NameSensitivityRange mg·kg-1Temperature range / ℃Humidity range / RH%Service life a
MIX 1008

Rs (in air) / Rs (in 1000 mg·kg-1 H2)

≥5

100-100020±255±55
MQ-8

Rs (in air) / Rs (in 1000 mg·kg-1 H2)

≥5

100-100020±255±510
MQ-2Rs (in air) / Rs (in 1000 mg·kg-1 C3H8)≥5300-1000020±265±510
Table 6  Parameter of semiconducting metal–oxide hydrogen sensor
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