CN105806739A - Sensor for detecting content of hydrogen in submarine hydrothermal solution fluid in situ - Google Patents
Sensor for detecting content of hydrogen in submarine hydrothermal solution fluid in situ Download PDFInfo
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- CN105806739A CN105806739A CN201610161658.XA CN201610161658A CN105806739A CN 105806739 A CN105806739 A CN 105806739A CN 201610161658 A CN201610161658 A CN 201610161658A CN 105806739 A CN105806739 A CN 105806739A
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Abstract
The invention relates to a sensor for detecting the content of hydrogen in submarine hydrothermal solution fluid in situ. The hydrogen sensor is composed of a hydrogen semipermeable membrane, a breathable gasket, a gas pressure sensor, a pressure test and data acquisition recorder and the like. The external to-be-detected hydrothermal solution fluid and an internal gas path are separated through the hydrogen semipermeable membrane supported by the breathable gasket, when hydrogen reaches osmotic equilibrium on the two sides of the membrane, partial pressure of hydrogen in the internal gas path is relevant to the content of hydrogen in the fluid, and therefore the content of hydrogen in the fluid is acquired by measuring the pressure of the gas path. The pressure of the gas path is observed through the gas pressure sensor and recorded by the pressure test and data acquisition recorder. The hydrogen sensor converts detection of the content of hydrogen in the hydrothermal solution fluid into observation of the gas pressure of the gas path through the hydrogen semipermeable membrane, and can be used for detecting the content of hydrogen in the high-temperature high-pressure submarine hydrothermal solution fluid in situ and also used for detecting the content of hydrogen in other normal-temperature normal-pressure and even high-temperature high-pressure fluid in situ.
Description
Technical field
The invention belongs to submarine hydrothermal solution fluid in situ detection technical field, be specifically related to a kind of can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid.
Background technology
Hydrothermal activity is there is in seabed.The substantially process of submarine hydrothermal activity is to ooze under cold sea water, and sea water is heated by country rock in underground, carries out mass exchange with country rock simultaneously, and the sea water (being now called hydrothermal fluid) after evolution is again to concentrate the form return surface, seabed of stream or Dispersed Flows[1].The content of hydrogen is the important parameter of hydrothermal fluid, and it reflects the redox state of Hydrothermal System Water-rock interaction system[2].Therefore in submarine hydrothermal solution fluid, the content of hydrogen also becomes the content that many correlational studyes are paid close attention to.
In hydrothermal fluid, the detection method of hydrogen content mainly has two kinds.One is the fluid sampler collected specimens utilizing and protecting gas, the content of hydrogen in in-site measurement fluid aboard ship.The method is method conventional at present, and its shortcoming is to rely on investigation and sampling equipment, is difficult to obtain high-resolution time series data.Two is utilize sensor to detect in position.The method observed efficiency is higher, and can be used for carrying out long-term Continuous Observation.
At present, can be used for the sensor of hydrogen content in situ detection in submarine hydrothermal solution fluid is electrochemical hydrogen gas sensor.Such as, Ding and Seyfried[2]Pt electrode and YSZ-pH electrode is utilized to make hydrogen gas sensor, electric potential difference between this sensor electrode changes with the change of hydrogen fugacity in the hydrothermal fluid observed, and meet this special response pattern of energy, and linked together by Henry's constant and activity coefficient between hydrogen fugacity and hydrogen content, therefore, the content of hydrogen in hydrothermal fluid can be obtained by the electric potential difference between measurement electrode.Au electrode is utilized to have same effect with the hydrogen gas sensor that YSZ-pH electrode is made[3].Poor owing to responding under YSZ-pH electrode cryogenic conditions, therefore this hydrogen gas sensor is for the observation under the hydrothermal fluid condition of more than 150 DEG C.Ye Ying etc.[4]Proposing a kind of electrochemical hydrogen gas sensor being made up of metallic hydrogen electrode and metal/metal oxide reference electrode, it can be used for normal temperature and pressure to the observation of hydrogen content in aqueous solution under high-temperature and high-pressure conditions.Owing to electrochemical hydrogen gas sensor is when measuring, its electrode material directly contacts with hydrothermal fluid, and therefore its electrode material and the sensor response stability when long-term work there is a problem[5]。
The invention reside in the another kind of principle of employing and prepare hydrogen gas sensor, for the content of hydrogen in situ detection submarine hydrothermal solution fluid.The measurement parts of this hydrogen gas sensor are separated by film and fluid, thus have good long-time stability.
Reference material:
[1]AltJC.Subseafloorprocessesinmid-oceanridgehydrothermalsystems.InSeafloorHydrothermalSystems:Physical,Chemical,Biological,andGeologicalInteractions,GeophysicalMonographSeries91,S.Humphriset.al(eds.),1995:85-114.
[2]DingK,SeyfriedWEJr.InsitumeasurementofdissolvedH2inaqueousfluidatelevatortemperaturesandpressures.GeochimicaetCosmochimicaActa,1995,59:4769-4773.
[3]DingK,SeyfriedWEJr.GoldasahydrogensensingelectrodeforinsitumeasurementofdissolvedH2insupercriticalaqueousfluid.JournalofSolutionChemistry,1996,25:421-433.
[4] Ye Ying, Chen Ying, Zhou Huaiyang, Zhou Yuhang, Peng is diligent, Gu Linyi.Suitable in the electrochemical hydrogen gas sensor of High Temperature High Pressure, the patent No.: 02111369.6.State Intellectual Property Office of the People's Republic of China, 2002.
[5]DingK,SeyfriedWEJr.InsitumeasurementofpHanddissolvedH2inmid-oceanridgehydrothermalfluidsatelevatedtemperatureandpressures.Chem.Rev.,2007,107:601-622。
Summary of the invention
It is an object of the invention to provide and a kind of can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid.The present invention specifically includes a kind of hydrogen gas sensor being made up of hydrogen semipermeable membrane, ventilative pad, gas pressure sensor, stress test and data acquisition recorder etc..
The hydrogen gas sensor of the present invention is different from electrochemical hydrogen gas sensor, it adopts hydrogen semipermeable membrane hydrothermal fluid and gas circuit to be separated, when hydrogen reaches Osmotic balance in film both sides, in gas circuit, the dividing potential drop of hydrogen is relevant with the content of hydrogen in fluid, therefore can obtain the content of hydrogen in fluid by the dividing potential drop of hydrogen in measurement gas circuit.When in gas circuit, the content of other gas can be ignored, the dividing potential drop of hydrogen is approximate equal with the gross pressure of gas, and available gas pressure transducer is observed.
What the present invention proposed can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, it is made up of end cap 1, battery 3, power line 4, stress test and data acquisition recorder 5, electric 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 pad 14 and hydrogen semipermeable membrane 15, wherein: stress test is installed in the cavity of electric chamber cylinder 6 with data acquisition recorder 5 and battery 3, stress test is connected with battery 3 by power line 4 with data acquisition recorder 5；Cylinder 6 one end, electric chamber is connected with end cap 1, and the other end is connected with air chamber cylinder 10, and one end that electric chamber cylinder 6 is connected with air chamber cylinder 10 arranges air chamber end cap 8, for sealed electrical air cavity cylinder 6；Gas pressure sensor 11 is installed in the cavity of air chamber cylinder 10, for observing the pressure of the empty intracavity gas of air chamber cylinder 10；Gas pressure sensor 11 is connected with data acquisition recorder 5 with stress test by described signal transmssion line 7 through air chamber end cap 8；Ventilative pad 14 is installed in mounting seat 13, and hydrogen semipermeable membrane 15 is installed on outside ventilative pad 14, and hydrogen semipermeable membrane 15 outward flange adopts with mounting seat 13 junction and is tightly connected, and mounting seat 13 is connected with air chamber cylinder 10 by gas delivery tube 12；When mounting seat 13 is placed in hydrothermal fluid, only hydrogen is diffused into by hydrogen semipermeable membrane 15 in the space of ventilative pad 14, is diffused to by gas delivery tube 12 further in the cavity of air chamber cylinder 10.
In the present invention, described electric chamber cylinder 6 and end cap junction arrange the first O 2, play sealing function.
In the present invention, described electric chamber cylinder 6 and air chamber cylinder 10 junction arrange the second O 9, play sealing function.
In the present invention, described end cap 1, electric chamber cylinder 6, air chamber end cap 8, air chamber cylinder 10, gas delivery tube 12 and mounting seat 13 process by titanium alloy material；Ventilative pad 14 is made up of titanium metal powder sintering.
In the present invention, described hydrogen semipermeable membrane 15 is made up of Pt or Ag-Pd alloy.
The hydrogen gas sensor work process of the present invention is as follows:
(1) by ready for this sensor, stress test and data acquisition recorder 5 are opened；By operation submersible into this sensor brought seabed and its mounting seat 13(is fixed with ventilative pad 14 and hydrogen semipermeable membrane 15) insert in hydrothermal vent and keep a period of time, treat that the hydrogen in hydrothermal vent fluid spreads through hydrogen semipermeable membrane 15 and reaches balance, simultaneously by the temperature of other means observation hydrothermal vent fluid and pressure；Hydrogen diffusion causes that air chamber cylinder 10 intracavity gas pressure change, and for stress test and 5 observations of data acquisition recorder and record；
(2) this sensor is recycled on research ship by operation submersible, opens end cap 1, stops stress test and data acquisition recorder 5, and data stress test and data acquisition recorder 5 recorded derive；End cap 1 and electric chamber cylinder 6 are sealed installation, and sensor is treated to use next time；
(3) pressure data time according to the diffusive equilibrium of record, hydrothermal vent temperature and pressure data, according to the conversion relation of sensor observed pressure with fluid hydrogen content, conversion obtains the content of hydrogen in the hydrothermal fluid observed.
The beneficial effects of the present invention is: the content of hydrogen in hydrothermal fluid is converted into the observation of gas pressure, and the sensor of observed pressure is placed in cavity and does not contact with fluid, thus has good long-time stability.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention；It is bolted between end cap 1 and electric chamber cylinder 6, between air chamber end cap 8 and air chamber cylinder 10 and between air chamber cylinder 10 and electric chamber cylinder 6, not shown.
Number in the figure: 1-end cap；2-the first O；3-battery；4-power line；5-stress test and data acquisition recorder；6-electric chamber cylinder；7-signal transmssion line；8-air chamber end cap；9-the second O；10-air chamber cylinder；11-gas pressure sensor；12-gas delivery tube；13-mounting seat；14-breathes freely pad；15-hydrogen semipermeable membrane.
Detailed description of the invention
The present invention is further illustrated by the examples below in conjunction with accompanying drawing.
Embodiment 1: as it is shown in figure 1, described hydrogen gas sensor is made up of end cap the 1, first O 2, battery 3, power line 4, stress test and data acquisition recorder 5, electric chamber cylinder 6, signal transmssion line 7, air chamber end cap the 8, second O 9, air chamber cylinder 10, gas pressure sensor 11, gas delivery tube 12, mounting seat 13, ventilative pad 14 and hydrogen semipermeable membrane 15.Wherein, ventilative pad 14 is installed in mounting seat 13, and hydrogen semipermeable membrane 15 is installed on outside ventilative pad 14；Mounting seat 13 is connected with air chamber cylinder 10 by gas delivery tube 12；Gas pressure sensor 11 is installed in the chamber of air chamber cylinder 10, and air chamber end cap 8 is connected with air chamber cylinder 10；Gas pressure sensor 11 is connected with data acquisition recorder 5 with stress test by signal transmssion line 7 through air chamber end cap 8；Stress test is connected by power line 4 with battery 3 with data acquisition recorder 5, and they are mounted in the chamber of electric chamber cylinder 6；Air cavity cylinder 6 one end is connected with air chamber cylinder 10, and the other end is connected with end cap 1.
Described ventilative pad 14 is installed in mounting seat 13, in the same plane outside the two；Hydrogen semipermeable membrane 15 is installed on the ventilative outer rear flank of pad 14, and hydrogen semipermeable membrane 15 outward flange contacts with mounting seat 13, and passes through welded seal.When now mounting seat 13 being placed in hydrothermal fluid, only hydrogen can pass through in the space that hydrogen semipermeable membrane 15 diffuses into ventilative pad 14, and diffused to the intracavity of air chamber cylinder 10 further by gas delivery tube 12.
Described air chamber end cap 8 is connected with air chamber cylinder 10 and forms the high pressure resistant cavity of sealing, and gas pressure sensor 11 is installed in the chamber of air chamber cylinder 10, for observing the pressure of air chamber cylinder 10 intracavity gas.
Described air cavity cylinder 6 one end is sealed by air chamber cylinder 10 and the second O 9, and the other end is sealed by end cap 1 and the first O 2, forms high voltage bearing sealing cavity；Stress test is installed in the chamber of electric chamber cylinder 6 with data acquisition recorder 5 and battery 3；Gas pressure sensor 11 is connected by the signal transmssion line 7 through air chamber end cap 8 with data acquisition recorder 5 with stress test.Now, the pressure data of air chamber cylinder 10 intracavity of gas pressure sensor 11 observation will be observed and record by stress test and data acquisition recorder 5.
Described end cap 1, electric chamber cylinder 6, air chamber end cap 8, air chamber cylinder 10, gas delivery tube 12 and mounting seat 13 process by titanium alloy material；Ventilative pad 14 is made up of titanium metal powder sintering.
Described hydrogen semipermeable membrane 15 is made up of Pt or Ag-Pd alloy.
Being observed by the gas pressure sensor 11 being installed in air chamber cylinder 10 by the pressure of gas, observation data are by the stress test being arranged in electric chamber cylinder 6 and data acquisition recorder 5 record.Laboratory is by ready for this sensor on the coast, and sets up the conversion relation between observed pressure and hydrothermal fluid content.
When using the content of hydrogen in this hydrogen gas sensor in-situ observation hydrothermal fluid at flight number in investigating, the first step, open end cap 1, after opening stress test and data acquisition recorder 5, end cap 1 is installed again, prepare lower water.Second step, by operation submersible, this sensor is carried to submarine hydrothermal solution district, the selected hydrothermal vent needing observation, first observe the pressure at hydrothermal vent place and the temperature of spout fluid, operated by submersible again and this sensor mounting seat 13(be fixed with ventilative pad 14 and hydrogen semipermeable membrane 15) insert hydrothermal vent, now, hydrogen in hydrothermal fluid will be spread in air chamber cylinder 10 by hydrogen semipermeable membrane 15, hydrogen diffusion causes that the pressure in air chamber cylinder 10 changes, this pressure is observed by gas pressure sensor 11, and for stress test and 5 records of data acquisition recorder；After waiting for a period of time, the diffusion of hydrogen reaches balance, and operation submersible reclaims hydrogen gas sensor and brings it back on research ship.3rd step, takes back laboratory after hydrogen gas sensor fresh water flush, dries outer surface, opens end cap 1, stops stress test and data acquisition recorder 5, and data stress test and data acquisition recorder 5 recorded derive；End cap 1 and electric chamber cylinder 6 are sealed installation, and sensor is treated to use next time.Finally, data being processed, pressure data during according to the diffusive equilibrium of record, hydrothermal vent temperature and pressure data, according to the conversion relation of sensor observed pressure with fluid hydrogen content, conversion obtains the content of hydrogen in the hydrothermal fluid observed.
Claims (5)
1. one kind can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, by end cap (1), battery (3), power line (4), stress test and data acquisition recorder (5), electric 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 pad (14) and hydrogen semipermeable membrane (15) composition, it is characterized in that: stress test is installed in the cavity in electric chamber cylinder (6) with data acquisition recorder (5) and battery (3), stress test is connected with battery (3) by power line (4) with data acquisition recorder (5)；Cylinder (6) one end, electric chamber is connected with end cap (1), the other end is connected with air chamber cylinder (10), one end that electric chamber cylinder (6) is connected with air chamber cylinder (10) arranges air chamber end cap (8), for sealed electrical air cavity cylinder (6)；Gas pressure sensor (11) is installed in the cavity of air chamber cylinder (10), is used for observing the pressure of the empty intracavity gas of air chamber cylinder (10)；Gas pressure sensor (11) is connected with data acquisition recorder (5) with stress test by described signal transmssion line (7) through air chamber end cap (8)；Ventilative pad (14) is installed in mounting seat (13), hydrogen semipermeable membrane (15) is installed on ventilative pad (14) outside, hydrogen semipermeable membrane (15) outward flange adopts with mounting seat (13) junction and is tightly connected, and mounting seat (13) is connected with air chamber cylinder (10) by gas delivery tube (12)；When mounting seat (13) is placed in hydrothermal fluid, only hydrogen is diffused into by hydrogen semipermeable membrane (15) in the space of ventilative pad (14), is diffused to by gas delivery tube (12) further in the cavity of air chamber cylinder (10).
2. according to claim 1 can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, it is characterized in that described electric chamber cylinder (6) and end cap (1) junction arrange the first O (2), play sealing function.
3. according to claim 1 can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, it is characterized in that described electric chamber cylinder (6) and air chamber cylinder (10) junction arrange the second O (9), play sealing function.
4. according to claim 1 can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, it is characterised in that described end cap (1), electric chamber cylinder (6), air chamber end cap (8), air chamber cylinder (10), gas delivery tube (12) and mounting seat (13) process by titanium alloy material；Ventilative pad (14) is made up of titanium metal powder sintering.
5. according to claim 1 can be used for the sensor of hydrogen content in situ detection submarine hydrothermal solution fluid, it is characterised in that described hydrogen semipermeable membrane (15) is made up of Pt or Ag-Pd alloy.
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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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| CN105806739B CN105806739B (en) | 2018-10-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110824111A (en) * | 2019-10-30 | 2020-02-21 | 同济大学 | Device for testing and correcting high-temperature high-pressure gas sensor |
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2016
- 2016-03-22 CN CN201610161658.XA patent/CN105806739B/en not_active Expired - Fee Related
Patent Citations (4)
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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 |
| CN102460111A (en) * | 2009-06-24 | 2012-05-16 | 因菲康有限公司 | Hydrogen sensor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110824111A (en) * | 2019-10-30 | 2020-02-21 | 同济大学 | Device for testing and correcting high-temperature high-pressure gas sensor |
| 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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