CN105806739B - A kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid - Google Patents
A kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid Download PDFInfo
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- CN105806739B CN105806739B CN201610161658.XA CN201610161658A CN105806739B CN 105806739 B CN105806739 B CN 105806739B CN 201610161658 A CN201610161658 A CN 201610161658A CN 105806739 B CN105806739 B CN 105806739B
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- G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
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Abstract
The present invention relates to a kind of hydrogen gas sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, which is made of hydrogen semi-permeable membrane, ventilative gasket, gas pressure sensor, pressure test and data acquisition recorder etc..Wherein, external hydrothermal fluid to be detected is separated with inner air path by the hydrogen semi-permeable membrane for pad support of breathing freely, when hydrogen is when film both sides reach osmotic equilibrium, the partial pressure of hydrogen is related with the content of hydrogen in fluid in inner air path, therefore obtains the content of hydrogen in fluid by measuring the pressure of gas circuit.The pressure of gas circuit is observed by gas pressure sensor, and is recorded by pressure test and data acquisition recorder.The hydrogen gas sensor converts the detection of hydrogen content in hydrothermal fluid to the observation to gas-circuit gas pressure by the semi-permeable membrane of hydrogen, it cannot be only used for the content of hydrogen in the in situ detection high temperature and pressure hydrothermal fluid of seabed, it can also be used to the in situ detection of hydrogen content in other normal temperature and pressures to high-temperature, high pressure fluid.
Description
Technical field
The invention belongs to submarine hydrothermal solution fluid in situ detection technical fields, and in particular to one kind can be used in situ detection seabed
The sensor of hydrogen content in hydrothermal fluid.
Background technology
In seabed, there are hydrothermal activities.The substantially process of submarine hydrothermal activity is oozed under cold seawater, and seawater is in underground quilt
Country rock heats, while carrying out mass exchange, the seawater after evolution with country rock（It is known as hydrothermal fluid at this time）Again with concentration stream or more
The form of diffusing returns to seabed surface[1].The content of hydrogen is the important parameter of hydrothermal fluid, it reflects Hydrothermal System water rock
The redox state of reaction system[2].Therefore the content of hydrogen also becomes many correlative studys concern in submarine hydrothermal solution fluid
Content.
In hydrothermal fluid there are mainly two types of the detection methods of hydrogen content.First, acquiring sample using the fluid sampler for protecting gas
Product, aboard ship in in-site measurement fluid hydrogen content.This method is currently used method, the disadvantage is that relying on investigation and taking
Sample equipment, it is difficult to obtain high-resolution time series data.Second is that being detected in situ using sensor.This method is observed
Efficiency is higher, and can be used for carrying out long-term continuous observation.
Currently, the sensor that can be used for hydrogen content in situ detection in submarine hydrothermal solution fluid is electrochemical hydrogen gas sensor.
For example, Ding and Seyfried[2]Hydrogen gas sensor is made using Pt electrodes and YSZ-pH electrodes, between the sensor electrode
Potential difference changes with the variation of hydrogen fugacity in the hydrothermal fluid observed, and meet can this special response pattern, and hydrogen
It is linked together by Henry's constant and activity coefficient between fugacity and hydrogen content, it therefore, can be by between measuring electrode
Potential difference obtains the content of hydrogen in hydrothermal fluid.Have using hydrogen gas sensor made of Au electrodes and YSZ-pH electrodes same
The effect of sample[3].Poor due to being responded under YSZ-pH electrode cryogenic conditions, which is used for 150 DEG C or more of heat
Observation under the conditions of liquid.Ye Ying etc.[4]It is proposed a kind of electricity being made of metal hydrogen electrode and metal/metal oxide reference electrode
Chemical hydrogen gas sensor, it can be used for the observation of hydrogen content in aqueous solution under normal temperature and pressure to high-temperature and high-pressure conditions.Due to electricity
When measuring, electrode material is directly in contact with hydrothermal fluid chemical hydrogen gas sensor, therefore its electrode material and sensing
Stability of the device response in long-term work there is a problem[5]。
The invention reside in hydrogen gas sensor is prepared using another principle, for hydrogen in situ detection submarine hydrothermal solution fluid
Content.The measuring part of the hydrogen gas sensor is separated by film and fluid, thus has preferable long-time stability.
Reference：
[1]Alt J C. Subseafloor processes in mid-ocean ridge hydrothermal
systems. In Seafloor Hydrothermal Systems: Physical, Chemical, Biological,
and Geological Interactions, Geophysical Monograph Series 91, S. Humphris
et.al (eds.), 1995: 85-114.
[2]Ding K, Seyfried W E Jr. In situ measurement of dissolved H2 in
aqueous fluid at elevator temperatures and pressures. Geochimica et
Cosmochimica Acta, 1995, 59: 4769-4773.
[3] Ding K, Seyfried W E Jr. Gold as a hydrogen sensing electrode for
in situ measurement of dissolved H2 in supercritical aqueous fluid. Journal
of Solution Chemistry, 1996, 25: 421-433.
[4]Ye Ying, Chen Ying, Zhou Huaiyang, Zhou Yuhang, Peng is diligent, Gu Linyi.Electrochemical hydrogen suitable for high temperature and pressure senses
Device, the patent No.：02111369.6.State Intellectual Property Office of the People's Republic of China, 2002.
[5]Ding K, Seyfried W E Jr. In situ measurement of pH and dissolved
H2 in mid-ocean ridge hydrothermal fluids at elevated temperature and
pressures. Chem. Rev., 2007, 107: 601-622。
Invention content
The purpose of the present invention is to provide a kind of sensors can be used for hydrogen content in situ detection submarine hydrothermal solution fluid.
The present invention is specifically included by hydrogen semi-permeable membrane, ventilative gasket, gas pressure sensor, pressure test and data acquisition recorder etc.
A kind of hydrogen gas sensor constituted.
The hydrogen gas sensor of the present invention is different from electrochemical hydrogen gas sensor, it use hydrogen semi-permeable membrane by hydrothermal fluid and
Gas circuit separates, and when hydrogen is when film both sides reach osmotic equilibrium, in gas circuit there is the content of hydrogen in the partial pressure of hydrogen and fluid
It closes, therefore the content of hydrogen in fluid can be obtained by measuring the partial pressure of hydrogen in gas circuit.When the content of other gases in gas circuit
When can ignore, the partial pressure of hydrogen is approximate equal with the gross pressure of gas, the observation of available gas pressure sensor.
The sensor proposed by the present invention that can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, by end cap 1, battery
3, power cord 4, pressure test and data acquisition recorder 5, electrical chamber cylinder 6, signal transmssion line 7, air chamber end cap 8, gas
15 groups of chamber cylinder 10, gas pressure sensor 11, gas delivery tube 12, mounting seat 13, ventilative gasket 14 and hydrogen semi-permeable membrane
At, wherein：Pressure test and data acquisition recorder 5 and battery 3 are installed in the cavity of electrical chamber cylinder 6, pressure test with
Data acquisition recorder 5 is connect by power cord 4 with battery 3；Electrical 6 one end of chamber cylinder is connect with end cap 1, the other end and gas
Chamber cylinder 10 connects, one end setting air chamber end cap 8 that electrical chamber cylinder 6 is connect with air chamber cylinder 10, electrical for sealing
Chamber cylinder 6；Gas pressure sensor 11 is installed in the cavity of air chamber cylinder 10, the cavity for observing air chamber cylinder 10
The pressure of interior gas；The signal transmssion line 7 passes through air chamber end cap 8 by gas pressure sensor 11 and pressure test and data
Acquisition and recording instrument 5 connects；Ventilative gasket 14 is installed in mounting seat 13, and hydrogen semi-permeable membrane 15 is installed on outside ventilative gasket 14
Side, for 15 outer edge of hydrogen semi-permeable membrane with 13 junction of mounting seat using being tightly connected, mounting seat 13 passes through gas delivery tube
12 are connected with air chamber cylinder 10；When mounting seat 13 is placed in hydrothermal fluid, only hydrogen is expanded by hydrogen semi-permeable membrane 15
It dissipates and enters in the gap for gasket 14 of breathing freely, further diffused to by gas delivery tube 12 in the cavity of air chamber cylinder 10.
In the present invention, the first O-ring 2 is arranged with end cap junction in the electrical chamber cylinder 6, plays sealing function.
In the present invention, the second O-ring 9 is arranged with 10 junction of air chamber cylinder in the electrical chamber cylinder 6, plays sealing and makees
With.
In the present invention, the end cap 1, electrical chamber cylinder 6, air chamber end cap 8, air chamber cylinder 10, gas delivery tube 12
It is process by titanium alloy material with mounting seat 13；Ventilative gasket 14 is made of titanium metal powder sintering.
In the present invention, the hydrogen semi-permeable membrane 15 is made of Pt or Ag-Pd alloys.
The hydrogen gas sensor course of work of the present invention is as follows：
（1）The sensor is ready, Opening pressure test and data acquisition recorder 5；It should by operation submersible
Sensor brings seabed into and by its mounting seat 13（It is fixed with ventilative gasket 14 and hydrogen semi-permeable membrane 15）It is placed in hydrothermal vent
And kept for a period of time, it waits for that the hydrogen in hydrothermal vent fluid spreads through hydrogen semi-permeable membrane 15 and reaches balance, passes through simultaneously
The temperature and pressure of other means observation hydrothermal vent fluids；Hydrogen diffusion causes 10 intracavity gas pressure of air chamber cylinder to become
Change, and is observed and recorded by pressure test and data acquisition recorder 5；
（2）The sensor is recycled on research ship by operation submersible, opens end cap 1, is stopped pressure test and is adopted with data
Collect recorder 5, and the data that pressure test and data acquisition recorder 5 are recorded export；End cap 1 and electrical chamber cylinder 6 is close
Envelope installation, sensor wait for using next time；
（3）Pressure data, hydrothermal vent temperature and pressure data when according to the diffusion balance of record, see according to sensor
The conversion relation of measuring pressure and fluid hydrogen content, conversion obtain the content of hydrogen in observed hydrothermal fluid.
The beneficial effects of the present invention are：It converts the content of hydrogen in hydrothermal fluid to the observation of gas pressure, observes
The sensor of pressure is placed in cavity not to be contacted with fluid, thus has preferable long-time stability.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention；Between end cap 1 and electrical chamber cylinder 6, air chamber end cap 8 and air chamber cylinder
It is bolted, is not shown in figure between body 10 and between air chamber cylinder 10 and electrical chamber cylinder 6.
Figure label：1- end caps；The first O-rings of 2-；3- batteries；4- power cords；5- pressure tests and data acquiring and recording
Instrument；The electrical chamber cylinders of 6-；7- signal transmssion lines；8- air chamber end caps；The second O-rings of 9-；10- air chamber cylinders；11- gas pressures
Force snesor；12- gas delivery tubes；13- mounting seats；14- breathes freely gasket；15- hydrogen semi-permeable membranes.
Specific implementation mode
It is further illustrated the present invention below by embodiment combination attached drawing.
Embodiment 1：As shown in Figure 1, the hydrogen gas sensor is by end cap 1, the first O-ring 2, battery 3, power cord 4, pressure
Test and data acquisition recorder 5, electrical chamber cylinder 6, signal transmssion line 7, air chamber end cap 8, the second O-ring 9, air chamber cylinder
Body 10, gas pressure sensor 11, gas delivery tube 12, mounting seat 13, ventilative gasket 14 and hydrogen semi-permeable membrane 15 form.Its
In, ventilative gasket 14 is installed in mounting seat 13, and hydrogen semi-permeable membrane 15 is installed on 14 outside of ventilative gasket；Mounting seat 13 is logical
Gas delivery tube 12 is crossed with air chamber cylinder 10 to be connected；Gas pressure sensor 11 is installed in the chamber of air chamber cylinder 10, gas
Body cavity end cap 8 is connect with air chamber cylinder 10；Signal transmssion line 7 passes through air chamber end cap 8 by gas pressure sensor 11 and pressure
Power test is connect with data acquisition recorder 5；Pressure test is connect with data acquisition recorder 5 with battery 3 by power cord 4,
They are mounted in the chamber of electrical chamber cylinder 6；6 one end of air cavity cylinder is connect with air chamber cylinder 10, and the other end connects with end cap 1
It connects.
The ventilative gasket 14 is installed in mounting seat 13, in the same plane on the outside of the two；Hydrogen semi-permeable membrane 15
After being installed on 14 outside of ventilative gasket, 15 outer edge of hydrogen semi-permeable membrane is contacted with mounting seat 13, and passes through welded seal.At this time
When mounting seat 13 is placed in hydrothermal fluid, only hydrogen can diffuse into the sky of ventilative gasket 14 by hydrogen semi-permeable membrane 15
In gap, and the intracavitary of air chamber cylinder 10 is further diffused to by gas delivery tube 12.
The air chamber end cap 8 connect with air chamber cylinder 10 and forms the high pressure resistant cavity of sealing, gas pressure sensing
Device 11 is installed in the chamber of air chamber cylinder 10, the pressure for observing 10 intracavity gas of air chamber cylinder.
Described 6 one end of air cavity cylinder is sealed by air chamber cylinder 10 and the second O-ring 9, and the other end passes through end cap 1 and the
One O-ring 2 seals, and forms high voltage bearing seal cavity；Pressure test is installed on electrically with data acquisition recorder 5 with battery 3
In the chamber of chamber cylinder 6；Gas pressure sensor 11 is with pressure test with data acquisition recorder 5 by passing through air chamber end cap 8
Signal transmssion line 7 connect.At this point, the pressure data for 10 intracavitary of air chamber cylinder that gas pressure sensor 11 is observed will be pressed
Power, which is tested, to be observed and records with data acquisition recorder 5.
The end cap 1, electrical chamber cylinder 6, air chamber end cap 8, air chamber cylinder 10, gas delivery tube 12 and mounting seat
13 are process by titanium alloy material；Ventilative gasket 14 is made of titanium metal powder sintering.
The hydrogen semi-permeable membrane 15 is made of Pt or Ag-Pd alloys.
The pressure of gas is observed by the gas pressure sensor 11 being installed in air chamber cylinder 10, observation data are by pacifying
Pressure test in electrical chamber cylinder 6 is recorded with data acquisition recorder 5.Laboratory prepares the sensor just on the coast
Thread, and establish the conversion relation between observed pressure and hydrothermal fluid content.
When in being investigated in flight number using the content of hydrogen in the hydrogen gas sensor in-situ observation hydrothermal fluid, the first step,
End cap 1 is opened, Opening pressure test installs end cap 1 with after data acquisition recorder 5 again, prepares lower water.Second step, by making
Industry submersible carries the sensor to submarine hydrothermal solution area, and the selected hydrothermal vent for needing to observe first is observed at hydrothermal vent
The temperature of pressure and spout fluid, then operated the sensor mounting seat 13 by submersible（It is fixed with 14 He of ventilative gasket
Hydrogen semi-permeable membrane 15）It is placed in hydrothermal vent, at this point, hydrogen in hydrothermal fluid will be by hydrogen semi-permeable membrane 15 to air chamber cylinder
It is spread in 10, hydrogen diffusion causes the pressure change in air chamber cylinder 10, the pressure to be observed by gas pressure sensor 11,
And it is recorded by pressure test and data acquisition recorder 5；After waiting for a period of time, the diffusion of hydrogen reaches balance, and operation is latent
Hydrophone recycles hydrogen gas sensor and brings it back on research ship.Third walks, and experiment is taken back after hydrogen gas sensor is rinsed with fresh water
Outer surface is dried in room, opens end cap 1, stops pressure test and data acquisition recorder 5, and pressure test and data acquisition are remembered
Record the data export that instrument 5 records；End cap 1 and the sealing of electrical chamber cylinder 6 are installed, sensor waits for using next time.Finally, logarithm
According to being handled, pressure data, hydrothermal vent temperature and pressure data when being balanced according to the diffusion of record are seen according to sensor
The conversion relation of measuring pressure and fluid hydrogen content, conversion obtain the content of hydrogen in observed hydrothermal fluid.
Claims (4)
1. a kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, by end cap (1), battery (3), power supply
Line (4), pressure test and data acquisition recorder (5), electrical chamber cylinder (6), signal transmssion line (7), air chamber end cap (8),
Air chamber cylinder (10), gas pressure sensor (11), gas delivery tube (12), mounting seat (13), ventilative gasket (14) and
Hydrogen semi-permeable membrane (15) forms, it is characterised in that：Pressure test is installed on electrically with data acquisition recorder (5) and battery (3)
In the cavity of chamber cylinder (6), pressure test is connect by power cord (4) with battery (3) with data acquisition recorder (5)；Electrically
Chamber cylinder (6) one end is connect with end cap (1), and the other end is connect with air chamber cylinder (10), electrical chamber cylinder (6) and air chamber cylinder
One end setting air chamber end cap (8) of body (10) connection, for sealing electrical chamber cylinder (6)；Gas pressure sensor (11) is pacified
In cavity loaded on air chamber cylinder (10), the pressure of the empty intracavity gas for observing air chamber cylinder (10)；The signal
Transmission line (7) passes through air chamber end cap (8) to connect gas pressure sensor (11) and pressure test with data acquisition recorder (5)
It connects；Ventilative gasket (14) is installed in mounting seat (13), and hydrogen semi-permeable membrane (15) is installed on the outside of ventilative gasket (14), hydrogen
For semi-permeable membrane (15) outer edge with mounting seat (13) junction using being tightly connected, mounting seat (13) passes through gas delivery tube
(12) it is connected with air chamber cylinder (10)；When mounting seat (13) is placed in hydrothermal fluid, only hydrogen is semi-transparent by hydrogen
Film (15) diffuses into the gap of ventilative gasket (14), further diffuses to air chamber cylinder by gas delivery tube (12)
(10) in cavity, the end cap (1), electrical chamber cylinder (6), air chamber end cap (8), air chamber cylinder (10), gas transport
Pipe (12) and mounting seat (13) are process by titanium alloy material；Ventilative gasket (14) is made of titanium metal powder sintering.
2. the sensor according to claim 1 that can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, feature
It is that the first O-ring (2) is arranged with end cap (1) junction in the electrical chamber cylinder (6), plays sealing function.
3. the sensor according to claim 1 that can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, feature
It is that the second O-ring (9) is arranged with air chamber cylinder (10) junction in the electrical chamber cylinder (6), plays sealing function.
4. the sensor according to claim 1 that can be used for hydrogen content in situ detection submarine hydrothermal solution fluid, feature
It is that the hydrogen semi-permeable membrane (15) is made of Pt or Ag-Pd alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610161658.XA CN105806739B (en) | 2016-03-22 | 2016-03-22 | A kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid |
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| CN201610161658.XA CN105806739B (en) | 2016-03-22 | 2016-03-22 | A kind of sensor can be used for hydrogen content in situ detection submarine hydrothermal solution fluid |
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| Publication Number | Publication Date |
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| CN105806739A CN105806739A (en) | 2016-07-27 |
| CN105806739B true CN105806739B (en) | 2018-10-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108333235A (en) * | 2018-04-24 | 2018-07-27 | 郑州迪邦科技有限公司 | Gas analyzer shell and the gas analyzer for using the shell |
| CN110824111B (en) * | 2019-10-30 | 2021-06-29 | 同济大学 | Device for testing and correcting high-temperature high-pressure gas sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10031882A1 (en) * | 2000-06-30 | 2002-01-10 | Leybold Vakuum Gmbh | Helium or hydrogen sensor |
| CN101750439A (en) * | 2008-12-19 | 2010-06-23 | 中国科学院大连化学物理研究所 | Hydrogen gas sensor based on thermal conduction principle |
| DE102009030180A1 (en) * | 2009-06-24 | 2010-12-30 | Inficon Gmbh | Hydrogen sensor |
| CN102297789B (en) * | 2011-05-27 | 2013-02-13 | 同济大学 | Original position time-sharing acquisition system for gas in deep seawater |
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