CN112362613A - Low-power-consumption small-volume long-term-duty deep-sea trace gas in-situ measuring instrument - Google Patents
Low-power-consumption small-volume long-term-duty deep-sea trace gas in-situ measuring instrument Download PDFInfo
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Abstract
The invention discloses a low-power consumption, small-volume and long-term on-duty deep sea trace gas in-situ measuring instrument, which comprises an external hanging unit, a measuring unit and a control unit, wherein the external hanging unit is detachably arranged outside a main body bin and is used for extracting trace gas dissolved in seawater for detection of the main body bin and diffusing waste gas generated after detection of the main body bin into degassed seawater; the main body bin is internally provided with an air inlet pump, a drying unit, an air detection unit and an exhaust pump, an air outlet of the external hanging unit is connected with an air inlet of the air detection unit after passing through the air inlet pump and the drying unit, and an air outlet of the air detection unit is connected with an air inlet of the external hanging unit through the exhaust pump. According to the external unit, the water-gas separation and the waste gas diffusion removal can be carried out in a non-interference synchronous mode, the main body bin and the external unit work independently, the possibility of water inflow caused by the fact that air tightness is influenced by manual misoperation and repeated opening and closing of the bin body is reduced, opening and air exchange maintenance are not needed, and long-term detection is achieved.
Description
Technical Field
The invention relates to the technical field of deep sea gas detection, in particular to a low-power-consumption small-volume long-term on-duty deep sea trace gas in-situ measuring instrument.
Background
Under the condition of energy shortage at present, the development of natural gas hydrate and oil gas resource detection technology has risen to the high degree of national strategy. Roughly estimating that the amount of hydrate prospect resources in sea areas and land areas of China is about 800 hundred million tons of oil equivalent, which is 2 times of the amount of conventional natural gas resources of China. The concentration of dissolved methane in the normally sedimented ocean bottom water is low and is 0.5-2nmolL-1However, in sea areas with natural gas hydrates, oil and gas reservoirs and ocean ridge hydrothermal systems and organic rich anaerobic sediments, a large amount of methane is produced in the lower part of the sediment and enters the bottom water through seepage or diffusion to be continuously mixed with the surrounding seawater to form a 'buoyancy plume' (buoyant plume). The buoyancy plume rises to a certain height from the sea bottom and is diffused and propagated in the horizontal direction after reaching density balance with surrounding seawater, so that methane plume (methane plume) which has a large horizontal area and is easy to detect is formed. The concentration of methane gas in the plume is significantly higher than that of the surrounding seawater, and the diffusion effect makes the abnormal distribution of the gas concentration in the seawater have certain regionality. By detecting the existence of the methane plume and tracking the diffusion path of the methane plume, indirect evidence can be provided for exploring favorable areas of natural gas hydrates and oil and gas resources.
The study of dissolved methane in seawater relies on the development of its measurement technique. The measurement means of field sampling-laboratory gas chromatography analysis is still the main measurement means of the concentration of dissolved methane in seawater at present, but the analysis method has the defects of ex-situ measurement, such as poor representativeness of the sampled product, inevitable pollution of the sample during the collection and pretreatment process, inevitable loss of dissolved methane during the storage and transportation of the sample, incapability of obtaining long-time sequence data and the like. Therefore, the long-term in-situ measurement technology with high precision and low power consumption is the development trend of the measurement technology of dissolved methane in seawater in the future. At present, the in-situ measurement technology for dissolved methane in seawater is mainly developed along two ideas, one of which is that methane gas dissolved in seawater is separated by a certain technical means, and the concentration of the methane gas is detected by using a gas sensor or an infrared absorption method; secondly, the in-situ sensor is aligned to the seawater containing methane gas for direct detection, such as evanescent wave principle and Raman spectrometer measurement. However, most of the sea areas in China have low background seawater methane concentration (generally in the order of nmol/L, and even lower than 1nmol/L in deep sea), the sensitivity and precision of the existing instruments are low, and taking a commercial dissolved methane sensor (METS) which is jointly developed and produced by Germany GKSS research center and Franatech company as an example, the detection precision is only 10nmol/L, only the measurement of methane with high concentration can be carried out, and the requirement of monitoring the background seawater methane abnormity cannot be met.
In recent years, with the improvement of the coating process of the high-reflection Cavity mirror, the Cavity ring-down Spectroscopy (CRDS) technology, including its derivative technologies, such as Integrated Cavity Output Spectroscopy (ICOS) and Cavity Enhanced Absorption Spectroscopy (CEAS), is rapidly widely used in the field of gas analysis. CRDS has the following characteristics: by measuring the attenuation rate of the transmitted light intensity instead of the intensity change after the light penetrates through the cavity, the measurement precision is not influenced by the fluctuation of the light source; the method is an absolute measurement method, complex and time-consuming calibration is not needed, the effective absorption path length is greatly increased through a high-precision optical resonant cavity, and high-sensitivity and high-selectivity measurement of target gas with volume concentration as low as parts per billion (ppb) level can be realized. Compared with methods based on chromatography and mass spectrometry, the CRD spectroscopy technology has the advantages of high sensitivity, fast response, lower cost and the like. The laser absorption spectrum technology gradually shows a certain potential in the application of marine complex environments due to the characteristics of low cost, high sensitivity and selectivity, good environmental adaptability and the like. In 2011, W.G. Lulzow et al detected dissolved methane and carbon dioxide in sea surface water in the sea area of the approach using an off-axis integrating cavity output spectrometer developed by Los Gatos Research, USA. The concentration of methane and its isotopic ratio in arctic seawater were measured by Uhilig and los, university of rhode island in 2017 using a G2201-i cavity ring-down spectrometer (CO 2, CH4 concentration and isotopic composition can be measured simultaneously) developed by PICARRO, usa. In 2018, Robert Grilli et al developed a CH4 dissolved gas spectrum analyzer in seawater by using an optical feedback cavity enhanced absorption spectrum technology, and evaluated the reliability of the system through laboratory correction and field application.
A methane detection instrument based on CRDS technology takes an American LRG deep sea methane ring-down spectrum detector as an example, components are integrated in a sealed pressure-resistant cylindrical shell, a water-proof breathable film for gas-liquid separation is arranged on the end face of the shell, and in practical application, the instrument has the following defects: 1. the permeable membrane is of a sheet structure, the effective contact area with seawater is small, the gas extraction efficiency is low, the single measurement time is 4-5 minutes, the permeable membrane is easily polluted by seawater, the working period is only 4-7 hours, the membrane needs to be replaced frequently, the possibility of water inflow caused by air tightness is influenced by frequent warehouse opening maintenance, and the safety of instruments is reduced. 2. The water proof ventilated membrane is as inside and outside connecting channel, and in order to guarantee infiltration efficiency, the thickness of the ventilated membrane is generally in the micron order of magnitude, and the breakage takes place very easily under the effect of external force, and in case the water proof ventilated membrane takes place the breakage, the sea water can directly get into inside the instrument, makes the instrument damage. 3. Waste gas (including detected gas or newly generated gas) generated in the detection process is stored in a gas storage and recovery mode, namely, the waste gas is stored and exhausted in the air after the instrument is recovered, and the continuous detection time of the deep-sea in-situ gas is greatly limited by the capacity of the waste gas pool. If a direct exhaust mode is adopted, in order to overcome the deep sea hydrostatic pressure, the front stage supercharging device needs to supercharge the waste gas to the pressure equivalent to the waste gas, for long-term continuous observation, the power supply of the instrument is supplied by a storage battery, the waste gas is discharged by the ultrahigh supercharging pump, the loss of electric quantity is accelerated, the loss is increased when the pressure of the supercharging pump is larger along with the increase of the depth of the sea water, and the service life of the instrument is shortened due to the consumption of the battery. Therefore, the conventional pressurization exhaust or air exhaust mode recovered to the water surface cannot meet the long-term continuous observation of deep sea trace gas.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the low-power-consumption small-volume long-term-duty deep-sea trace gas in-situ measuring instrument.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low power consumption, small volume and long-term on-duty deep sea trace gas in-situ measuring instrument comprises
The external hanging unit is detachably arranged outside the main body bin and is used for extracting trace gas dissolved in the seawater for detection of the main body bin and diffusing waste gas generated after detection of the main body bin into degassed seawater;
the main body bin is internally provided with an air inlet pump, a drying unit, an air detection unit and an exhaust pump, an air outlet of the external hanging unit is connected with an air inlet of the air detection unit after passing through the air inlet pump and the drying unit, and an air outlet of the air detection unit is connected with an air inlet of the external hanging unit through the exhaust pump.
Furthermore, a water-proof air-permeable film for preventing the main body bin from water inlet is arranged between the external hanging unit and the air inlet pump and between the external hanging unit and the air outlet pump. The setting of water proof ventilated membrane realizes the secondary protection in main part storehouse, guarantees the security of instrument.
Further, the plug-in unit comprises
The middle part of the shell is provided with a partition plate which divides the shell into a first barrel body used for degassing and a second barrel body used for exhausting, and the partition plate is provided with a one-way valve which enables the first barrel body to be communicated with the second barrel body in a one-way mode;
the gas-liquid separation rods are respectively arranged on the first barrel body and the second barrel body and comprise end covers, support rods, gas-liquid separation membranes and spiral sheets;
the end cover is hermetically connected with the end part of the barrel body to seal the barrel body, the support rod is made of porous loose materials, a cavity is arranged in the center, one end of the support rod is fixed on the end cover, the other end of the support rod is sealed, the gas-liquid separation membrane is wrapped on the outer side wall of the support rod, the spiral sheet is sleeved on the outer side of the gas-liquid separation membrane, and when the gas-liquid separation rod is fixed on the barrel body, the shell, the spiral sheet and the gas-liquid separation membrane form a spiral flow passage;
the center of the end cover is provided with a gas outlet communicated with the cavity of the support rod, the outer edge of the end cover is provided with a liquid inlet communicated with the spiral flow channel, the center of the end cover is provided with a gas inlet communicated with the cavity of the support rod, and the outer edge of the end cover is provided with a liquid outlet communicated with the spiral flow channel.
Further, the liquid inlet is connected with a filter core rod. The seawater to be measured is primarily filtered by the filter element rod, so that the pollution to the device caused by the introduction of large particles and organisms is reduced.
Further, the liquid outlet is connected with a water pump. And a driving force is provided, so that the seawater flows spirally in the barrel body to be fully contacted with the gas-liquid separation membrane.
Further, the liquid inlet and the liquid outlet are both provided with copper meshes. The arrangement of the copper mesh can prevent microorganisms from growing to block the pipeline.
Further, the porous loose material is air filtering stone. The size of the cavity of the support rod is reduced as much as possible while the pressure-bearing capacity of the gas-liquid separation membrane is improved, so that the gas permeability is improved.
Furthermore, the cavity of the support rod in the first barrel body and the pipeline connected with the cavity are filled with drying agents. Can carry out preliminary drying to the separation gas, be favorable to reducing the consumption of main part storehouse interior drying unit.
Further, the drying unit adopts a renewable dryer. Need not to open the storehouse and change the drier, reduce the problem of instrument maintenance security.
Further, the gas detection unit adopts a CRDS spectrum measurement system. By adopting the CRDS spectrum measuring system with high sensitivity, high repeatability and strong stability, the volume and the weight of the instrument are effectively reduced while the measuring precision is ensured.
Compared with the prior art, the invention has the beneficial effects that:
1. the main body bin and the external hanging unit are mutually independent, so that the instrument can be maintained without opening the bin, the possibility of water inflow caused by the fact that manual misoperation and repeated opening and closing of the bin body affect air tightness is reduced, the problem of instrument maintenance safety is solved, and long-term attendance of 4000 meters in maximum depth is realized.
2. The main body bin is not directly communicated with seawater, the gas inlet and outlet connected with the external hanging unit are provided with water-proof breathable films, and the external hanging unit is communicated with water in an open mode and is not affected by pressure, so that even if an accident happens when the external hanging unit is maintained, the seawater can be prevented from entering the expensive main body bin due to the secondary protection effect of the water-proof breathable films, and the safety of the instrument is further improved.
3. The external hanging unit adopts the combined design of the cylindrical gas-liquid separation membrane and the spiral flow channel, the contact ratio of the seawater and the membrane is increased, the contact area is improved by 80-200 times compared with that of the traditional method, the water-gas separation time is greatly shortened, and the single measurement time can be shortened to be within 1 minute.
4. The large contact ratio of the external hanging unit greatly reduces the water consumption for separating gas in unit volume, thereby effectively prolonging the service life of the gas-liquid separation membrane and the filter core rod, greatly prolonging the maintenance period of the product, realizing long-term watching of the measuring instrument, expanding the in-situ measurement period to be more than 6 months, solving the key problem of high-loss accessory dependence and realizing that the replacement of a single accessory is more than 12 months.
5. The external hanging unit adopts an integrated design of gas-water separation and waste gas diffusion and discharge, the discharged seawater can absorb waste gas more easily, the gas-water separation and the waste gas diffusion and discharge can be carried out in a non-interference synchronous mode, the waiting is not needed in the two-time measurement, the requirement of continuous measurement of deep sea trace gas is met, the warehouse opening and ventilation maintenance are not needed, and the long-term detection is realized.
6. The external hanging unit is internally provided with a common drying agent for primary drying of the separated gas, the main body bin is provided with a reducible drying agent for secondary drying of the separated gas, the drying agent does not need to be replaced by opening the bin, and the drying agent and the external hanging unit are combined, so that the gas drying effect is improved, the power consumption of the drying unit of the main body bin is reduced, and the long-term on duty of an instrument is facilitated.
Drawings
FIG. 1 is an external structural schematic diagram of the deep sea trace gas in-situ measuring instrument
FIG. 2 is a schematic diagram of the deep sea trace gas in-situ measuring instrument of the present invention;
FIG. 3 is an exploded view of the plug-in unit of the present invention;
FIG. 4 is a front sectional view of the external hanging unit of the present invention (with the filter cartridge and water pump omitted);
description of reference numerals: 1-plug-in unit; 11-a housing; 101-barrel I; 102-a second barrel body; 103-a separator; 104-a one-way valve; 12-a gas-liquid separation rod; 201-end cap; 202-a support bar; 203-gas-liquid separation membrane; 204-helical piece; 205-spiral flow channel; 206-a cavity; 13-a filter core rod; 14-a water pump; 2-a main body bin; 21-an intake pump; 22-a drying unit; 23-a gas detection unit; 24-an exhaust pump; 25-water-proof and breathable films; 26-a first three-way valve; 27-a second three-way valve; a 28-nitrogen tank; a-a gas outlet; b-a gas inlet; c-a liquid inlet; d-liquid outlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of embodiments of the present invention, and not all embodiments.
As shown in fig. 1 and 2, a low-power consumption, small-volume and long-term duty deep-sea trace gas in-situ measuring instrument includes an external unit 1 and a main body cabin 2 which can work independently and are connected with each other through a gas pipeline.
The external hanging unit 1 is used for realizing extraction of trace gas and diffusion and discharge of waste gas, specifically, on one hand, the permeable membrane is used for extracting the trace gas dissolved in seawater and conveying the trace gas to the main body bin 2 through a gas pipeline for detection, and on the other hand, the permeable membrane is used for diffusing the waste gas generated after the detection of the main body bin 2 into the degassed seawater, so that synchronous discharge of the waste gas is realized.
The main body bin 2 is used for detecting trace gas, and is internally provided with an air inlet pump 21, a drying unit 22, a gas detection unit 23 and an exhaust pump 24. The gas outlet of the external hanging unit 1 is connected with the gas inlet of the gas detection unit 23 after passing through the gas inlet pump 21 and the drying unit 22, and the gas outlet of the gas detection unit 23 is connected with the gas inlet of the external hanging unit 1 through the gas exhaust pump 24.
This application sets up the osmotic membrane of easy loss in external unit 1, and main part storehouse 2 is not direct to communicate with each other with the sea water, and one can avoid the sea water directly to get into main part storehouse 2, leads to inside device to damage, and two coming, waste gas passes through osmotic membrane diffusion exhaust, only needs to maintain external unit 1 at ordinary times, need not to open main part storehouse 2, can prevent frequently opening the storehouse and maintain the security that reduces the instrument.
In order to realize the secondary protection of the main body cabin 2 and further reduce the possibility of water inflow, water-resisting and air-permeable films 25 are arranged on the pipelines between the external hanging unit 1 and the air inlet pump 21 and between the exhaust pump 24 and the external hanging unit 1. Because the waterproof and breathable film 25 can not contact with seawater at ordinary times (only when the external hanging unit 1 leaks water, the waterproof and breathable film can contact with seawater), the replacement period is more than 1 year, and frequent replacement is not needed.
In order to further reduce the number of times of opening the warehouse, the drying unit 22 adopts a reproducible dryer, and the desiccant can be regenerated in an electric heating mode without opening the warehouse to replace the desiccant, thereby further reducing the problem of instrument maintenance safety.
It should be noted that the trace gas dissolved in seawater includes, but is not limited to, methane, carbon dioxide, carbon monoxide, hydrogen sulfide, nitrous oxide, etc., and since the present application focuses on the fields of natural gas hydrate and oil and gas resource detection, the following description will be given by taking methane as the gas to be measured.
As shown in fig. 3 and 4, the plug-in unit 1 of the present application is mainly composed of a housing 11 and gas-liquid separation rods 12 provided at both ends of the housing 11.
The gas-liquid separation rods 12 are two and have the same structure, one is arranged in the first barrel body 101 and used for quickly extracting methane dissolved in seawater, and the other is arranged in the second barrel body 102 and used for quickly diffusing and discharging waste gas generated after detection of the gas detection unit 23 of the main body bin 2.
According to henry's law, in a sealed container with a certain temperature, the partial pressure of gas is in direct proportion to the molar concentration of the gas dissolved in a solution, when the partial pressure of gas on one side is larger, the gas on the side permeates into the other side through a permeable membrane until the partial pressures of the gas on two sides of the permeable membrane reach equilibrium, and the degassing rate of the gas to be measured is related to parameters such as seawater temperature, seawater pressure, seawater methane partial pressure, seawater flow rate, permeable membrane area, permeable membrane thickness, gas bin volume, gas bin methane partial pressure and the like. To describe the diffusion process of dissolved methane from seawater through the permeable membrane into the gas silo, the following equation is given:
wherein, Pp(t) is the partial pressure of methane in the gas silo over time, t is the diffusion time, PF(T, h, q) is the partial pressure of methane in seawater (related to the temperature T, depth h and flow rate q of seawater, the permeation rate of methane increases with the increase of the flow rate q of the seawater, when the flow rate reaches a certain value, the permeation rate of methane increasesThe amplitude of the addition will decrease, and can even be considered as a constant value), R is the gas constant, V is the total volume of the gas compartment, A is the area contacting the seawater permeable membrane, L is the thickness of the permeable membrane, P is the volume of the gas compartmentTFor permeability coefficient related to the boundary layer resistance of dissolved methane, in general PT/PFWhen (T, h, q) is approximately 1, it is considered that seawater and methane in the gas silo are in equilibrium.
From the above equation, in order to realize the rapid diffusion equilibrium of methane, i.e. reduce the time t, the volume V of the gas bin can be reduced, the thickness L of the permeable membrane can be reduced, the area A of the permeable membrane can be increased, and the permeability coefficient P can be increasedTAnd the like. In contrast, the design of the gas-liquid separation rod 12 is to achieve the maximum contact ratio of seawater and the permeable membrane material on the premise of minimizing the volume of seawater.
Specifically, the gas-liquid separation rod 12 mainly includes an end cap 201, a support rod 202, a gas-liquid separation membrane 203, and a spiral piece 204. The end cap 201 is used for being hermetically connected with the end of the first barrel body 101 or the second barrel body 102 so as to seal the first barrel body 101 or the second barrel body 102. The support rod 202 is cylindrical, one end of the support rod is fixed at the center of the end cover 201, the other end of the support rod is closed, and the center of the support rod is provided with a cavity 206 used as a gas bin. Thus, the cavities 206 in the two barrels are not communicated with each other, the cavity 206 in the first barrel 101 is used as a gas bin for extracting methane, and the cavity 206 in the second barrel 102 is used as an exhaust gas bin. The gas-liquid separation membrane 203 is wrapped on the outer side wall of the support rod 202, the spiral sheet 204 is sleeved on the outer side of the gas-liquid separation membrane 203, and when the gas-liquid separation rod 12 is fixed on the shell 11, the inner wall of the first barrel body 101 or the second barrel body 102, the spiral sheet 204 and the outer wall of the gas-liquid separation membrane 203 form a spiral flow channel 205 for liquid to flow.
The end cover 201 is connected with the first barrel body 101, the center of the end cover is provided with a gas outlet a communicated with a cavity 206 in the end cover, and the outer edge of the end cover is provided with a liquid inlet c communicated with a spiral flow channel 205 in the end cover; the end cover 201 connected with the second barrel body 102 is provided with a gas inlet b communicated with the cavity 206 in the center and a liquid outlet d communicated with the spiral flow channel 205 on the outer edge. The gas outlet a is communicated with the gas inlet pump 21 after passing through the water-proof and breathable film 25 through a gas pipeline, and the gas exhaust pump 24 is communicated with the gas inlet b after passing through the other water-proof and breathable film 25 through the gas pipeline.
The support rod 202 is made of porous loose materials, can allow media such as liquid and gas to pass through, large-particle solids cannot pass through, and is used for supporting the gas-liquid separation membrane 203, so that the pressure bearing capacity is improved, the design of the support rod needs to adapt to a deep sea environment of not less than 4000 meters, in the embodiment, the porous loose materials are made of gas filtering stones, and the maximum pressure resistance of the gas-liquid separation rod 12 is achieved on the premise of meeting certain porosity.
The gas-liquid separation membrane 203 is generally a thin membrane made of Teflon AF 2400, high-density polyethylene fiber, modified polypropylene fiber, or the like, and has a certain elasticity. Due to the diffusion effect, the gas-liquid separation membrane 203 allows the middle volatile and semi-volatile dissolved gases in the water to pass through, but water molecules cannot pass through. The efficiency of extracting gas by the gas-liquid separation membrane 203 is positively correlated with the contact area of liquid and the membrane, compared with the conventional flaky permeable membrane, the contact area of the circular tubular gas-liquid separation membrane 203 is expanded to the whole cylindrical surface from a circular bottom surface, and meanwhile, the design of the spiral flow channel 205 can greatly increase the effective contact area while ensuring the flow uniformity of the liquid, improve 80-200 times compared with the traditional method, greatly shorten the time of water-gas separation, and shorten the single measurement time to within 1 minute.
Meanwhile, the water consumption for separating gas in unit volume of the gas-liquid separation membrane 203 with large contact ratio is greatly reduced, so that the service life of the gas-liquid separation membrane 203 and the filter element rod 13 can be effectively prolonged, the maintenance period of the external unit 1 can be greatly prolonged, the long-term watching of the measuring instrument is realized, and the in-situ measurement period is prolonged to be more than 6 months.
In order to ensure the safety of the instrument, the liquid inlet c is connected with a filter core rod 13, and the filter core rod 13 is used for carrying out primary filtration on the seawater, so that the pollution to the instrument caused by the introduction of large particles and organisms is reduced. In order to ensure the flow rate of seawater in the spiral flow channel 25 and increase the gas permeation rate, the liquid outlet d is connected to the water pump 14, so that seawater flows in from the liquid inlet c, and flows out from the liquid outlet d after the seawater flows spirally in the first barrel body 101 and the second barrel body 102.
External seawater enters the spiral flow channel 205 of the first barrel body 101 from the liquid inlet c, and then fully contacts the gas-liquid separation membrane 203, methane dissolved in the seawater enters the cavity 206 through the gas-liquid separation membrane 203 and the support rod 202, enters the gas detection unit 23 through the gas outlet a after being pumped by the air inlet pump 21 for detection, degassed seawater flows into the spiral flow channel 205 of the second barrel body 102 from the check valve 104 at the bottom of the first barrel body 101 and then fully contacts the gas-liquid separation membrane 203 of the second barrel body 102 again, meanwhile, waste gas generated after detection by the gas detection unit 23 enters the cavity 206 of the second barrel body 102 through the gas inlet b after being pumped by the exhaust pump 24, is diffused into the seawater through the support rod 202 and the gas-liquid separation membrane 203, and finally flows out from the liquid outlet d. Because the gas content is reduced after the seawater is degassed in the first barrel body 101 and the seawater is in a hungry state, when the water body flows to the second barrel body 102, the waste gas can be better permeated and carried away due to the increase of the gas permeation pressure, the synchronous operation of gas-water separation and waste gas diffusion discharge is ensured, and no waiting is needed between the two measurements.
During the methane extraction process, the gas inlet pump 21 continuously delivers the separated methane to the gas detection unit 23, and the gas inlet pump 21 is turned off until the pressure reaches a set value. In this process, the cavity 206 is always in a negative pressure state, so that the maximum pressure difference between both sides of the gas-liquid separation membrane 203 is ensured, and the maximum gas permeability is realized. Similarly, in the exhaust gas discharging process, the exhaust pump 21 is turned on to timely convey the exhaust gas generated after the detection of the gas detection unit 23 into the cavity 206 of the second barrel 102, so as to ensure that a sufficient pressure difference is formed between the exhaust gas and the partial pressure of the degassed seawater, and thus the exhaust gas is rapidly diffused and discharged.
Further, in order to prevent the growth of microorganisms to block the pipe, both the liquid inlet c and the liquid outlet d are provided with copper meshes. In order to reduce the spectrum absorption interference effect of water vapor in the seawater separation gas, a certain amount of drying agent is filled in the cavity 206 corresponding to the first barrel 101 and the gas pipeline connected with the cavity, so that the separation gas can be primarily dried, and the power consumption of the drying unit 22 for secondary drying in the main body bin 2 can be reduced.
In order to meet the requirement of the detection limit of deep-sea methane of 0.5nmol/L, the gas detection unit of the deep-sea methane detection device adopts a CRDS (CrDS) spectral measurement system which is high in sensitivity, repeatability and stability, and effectively reduces the size and weight of the instrument while ensuring high measurement precision.
The gas detection unit 3 mainly comprises a laser spectrum hardware system and an upper computer software system. The laser spectrum hardware system mainly comprises a mode-hopping-free DFB type tunable laser and a control unit thereof, an optical isolator, an acousto-optic modulator, a long-range ring-down cavity, a Fabry-Perot etalon, a photoelectric detector, and a gas sampling unit consisting of a drying tube, a flow and pressure controller and the like; an RS485 communication protocol is adopted in the upper computer software system, and Labview software is combined to realize automatic control of the system, real-time acquisition, display, analysis processing and storage of spectral data, a related signal denoising algorithm, laser frequency locking and the like.
The current in the laser is controlled by an additional current driving signal to realize the rapid tuning scanning of the output wavelength of the laser in the range of methane and water vapor absorption lines. When the optical ring-down cavity is designed, the inner wall is plated with a corrosion-resistant and adsorption-resistant quartz layer so as to reduce the influence of the adsorption of the inner wall on gas absorption measurement. In order to realize high-sensitivity measurement, two plano-concave high reflecting mirrors are selected as the cavity mirror, the reflectivity R of the cavity mirror is more than 99.98% in the wavelength tuning range, and the corresponding effective absorption optical path L is equal to L0/(1-R) is greater than the ring-down cavity geometric path length L05000 times of the total optical length, and the estimated effective total optical length can reach 5 km.
It is easy to understand, the measuring apparatu of this application not only can be used to deep sea methane and measure, still can be used to atmospheric methane for this reason, main part storehouse 2 is inside still to be provided with three-way valve one 26, three-way valve two 27 and nitrogen gas jar 28. The first port of the three-way valve 26 is connected with a water-proof and air-permeable film 25 at the inlet of the main body bin 2, the second port is connected with a nitrogen tank 28, and the third port is connected with an air inlet pump 21. The port I of the second three-way valve 27 is connected with an exhaust pump 24, the port II is connected with the interior of the main body bin 2, the port III is connected with a water-proof breathable film 25 at the outlet of the main body bin 2, and the conversion between the two measurement modes of atmospheric methane measurement and deep sea methane measurement can be realized by adjusting the valve positions of the first three-way valve 26 and the second three-way valve 27.
Atmospheric methane measurement mode: the first three-way valve 26 is in a state of sample injection from the second port and sample outlet from the third port; the second three-way valve 27 is in a state of firstly injecting samples from the inlet and secondly discharging samples from the outlet. Before atmospheric methane content measurement is performed, the gas detection unit 23 needs to be background-measured by nitrogen, and the principle is that the gas detection unit 23 enables nitrogen in a ring-down cavity to reach a certain pressure under the condition of a certain temperature and pressure, so that background measurement is performed. After the background measurement is completed, the pipeline of the nitrogen tank 28 is pulled out, so that the opening II of the three-way valve I26 is communicated with the outside, outside air enters the gas detection unit 23 after passing through the air inlet pump 21 and the drying unit 22, when the temperature and the pressure in the gas detection unit 23 reach certain conditions, the methane content is measured, and the measured air is discharged out of the instrument through the opening II of the air exhaust pump 24 and the three-way valve II 27.
Deep sea methane measurement mode: the first three-way valve 26 is in a state of sample injection from the port II and sample outlet from the port III, and the second three-way valve 27 is in a state of sample injection from the port III and sample outlet from the port III. When the background measurement is required, the background measurement can be performed on the gas detection unit 23 by the nitrogen tank 28, the principle of which is the same as above. After the background measurement is finished, the state of the first three-way valve 26 is adjusted, so that the sample is introduced from the first port and is discharged from the third port. The water pump 14 is started to introduce seawater, the seawater enters the spiral flow channel 205 of the barrel body I101 through the filter core rod 13 to flow spirally and fully contact with the gas-liquid separation membrane 203, the air inlet pump 21 is started to pump air to the corresponding cavity 206 in the flowing process of the seawater to generate negative pressure, methane molecules in the seawater are extracted to the pore space of the support rod 202 by the gas-liquid separation membrane 203 under the action of pressure difference, then pass through the support rod 202 to enter the cavity 206, and further enter the gas detection unit 23 through the gas outlet a, the drying agent in the pipeline, the water-proof breathable membrane 25, the three-way valve I26, the air inlet pump 21 and the drying unit 22, when the pressure and the temperature reach a certain condition, the gas detection unit 23 starts to measure the methane gas, in the measuring process, the microcomputer can collect, calculate and store data, after the measurement is completed, the air exhaust pump 21 is started, the waste gas detected in the gas detection unit 23 is pumped out of the ring-down cavity, and enters the cavity 206 of the second barrel body 102 through the second three-way valve 27, the water-proof and breathable film 25 and the gas inlet b, at this time, the degassed seawater flows into the spiral flow channel 205 of the second barrel body 102 from the one-way valve 104 at the bottom of the first barrel body 101, and fully contacts with the gas-liquid separation film 203 of the second barrel body 102 again, methane molecules (waste gas) in the cavity 206 of the second barrel body 102 are extracted to the interface between the seawater and the film by the gas-liquid separation film 203 under the action of pressure difference, are dissolved in the flowing seawater, and are finally discharged through the liquid outlet d, so that a measurement cycle is completed.
In conclusion, the deep sea trace gas in-situ measuring instrument solves the key problem of rapid sample injection and sample extraction under the condition of low power consumption of deep sea equipment, effectively reduces the volume and the weight of a sensing system by trace CH4 measurement based on a high-sensitivity cavity ring-down spectroscopy technology, and meets the requirements of long-term attendance at the maximum depth of 4000 meters and the detection limit of seawater methane of 0.5 nmol/L.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (10)
1. The utility model provides a low-power consumption small volume long-term deep sea trace gas normal position measuring apparatu of guarding which characterized in that: comprises that
The external hanging unit is detachably arranged outside the main body bin and is used for extracting trace gas dissolved in the seawater for detection of the main body bin and diffusing waste gas generated after detection of the main body bin into degassed seawater;
the main body bin is internally provided with an air inlet pump, a drying unit, an air detection unit and an exhaust pump, an air outlet of the external hanging unit is connected with an air inlet of the air detection unit after passing through the air inlet pump and the drying unit, and an air outlet of the air detection unit is connected with an air inlet of the external hanging unit through the exhaust pump.
2. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 1, wherein: and water-proof and breathable films for preventing the main body bin from water inlet are arranged between the external hanging unit and the air inlet pump and between the external hanging unit and the air outlet pump.
3. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 1, wherein: the plug-in unit comprises
The middle part of the shell is provided with a partition plate which divides the shell into a first barrel body used for degassing and a second barrel body used for exhausting, and the partition plate is provided with a one-way valve which enables the first barrel body to be communicated with the second barrel body in a one-way mode;
the gas-liquid separation rods are respectively arranged on the first barrel body and the second barrel body and comprise end covers, support rods, gas-liquid separation membranes and spiral sheets;
the end cover is hermetically connected with the end part of the barrel body to seal the barrel body, the support rod is made of porous loose materials, a cavity is arranged in the center, one end of the support rod is fixed on the end cover, the other end of the support rod is sealed, the gas-liquid separation membrane is wrapped on the outer side wall of the support rod, the spiral sheet is sleeved on the outer side of the gas-liquid separation membrane, and when the gas-liquid separation rod is fixed on the barrel body, the shell, the spiral sheet and the gas-liquid separation membrane form a spiral flow passage;
the center of the end cover is provided with a gas outlet communicated with the cavity of the support rod, the outer edge of the end cover is provided with a liquid inlet communicated with the spiral flow channel, the center of the end cover is provided with a gas inlet communicated with the cavity of the support rod, and the outer edge of the end cover is provided with a liquid outlet communicated with the spiral flow channel.
4. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 3, wherein: the liquid inlet is connected with a filter core rod.
5. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 3, wherein: the liquid outlet is connected with a water pump.
6. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 3, wherein: and the liquid inlet and the liquid outlet are both provided with copper nets.
7. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 3, wherein: the porous loose material is air filtering stone.
8. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 3, wherein: and a drying agent is filled in the cavity of the support rod in the first barrel body and the pipeline connected with the support rod.
9. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 1, wherein: the drying unit adopts a renewable dryer.
10. The low-power consumption small-volume long-term deep-sea trace gas in-situ measuring instrument according to claim 1, wherein: the gas detection unit adopts a CRDS spectrum measurement system.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114838975A (en) * | 2022-03-10 | 2022-08-02 | 浙江大学 | Deep sea fluid nozzle particle sampling device and sampling method thereof |
| CN114839318A (en) * | 2022-03-01 | 2022-08-02 | 中国海洋大学 | High-efficient degasification detecting system suitable for high pressure sea water underwater operation |
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