CN112645386A - Optical fiber hydrogen sensor, preparation method and hydrogen leakage detection device - Google Patents
Optical fiber hydrogen sensor, preparation method and hydrogen leakage detection device Download PDFInfo
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- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
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Abstract
The invention discloses an optical fiber hydrogen-sensitive sensor, a preparation method and a hydrogen leakage detection device, wherein the optical fiber hydrogen-sensitive sensor comprises an optical fiber sensor and a hydrogen-sensitive film coated on an optical fiber sensing area of the optical fiber sensor, the raw material formula of the hydrogen-sensitive film comprises a hydrogen-sensitive material and a binder, and the hydrogen-sensitive material is one or a combination of more of a titanium dioxide hydrogen-sensitive material and a tungsten trioxide hydrogen-sensitive material; the titanium dioxide hydrogen-sensitive material comprises tetrabutyl titanate and PdCl2Tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1; the tungsten trioxide hydrogen sensitive material comprises WO3And lanthanum nitrate, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40. The optical fiber hydrogen-sensitive sensor disclosed by the invention integrates a hydrogen-sensitive film and an optical fiber micro-processing technology, develops a software monitoring system, realizes full-coverage non-blind-area real-time monitoring, and solves the problems of more blind areas in local area detection, untimely leakage finding, large workload of manual routing inspection and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to an optical fiber hydrogen sensor, a preparation method and a hydrogen leakage detection device.
Background
In the energy law of China (a survey of comments) in the head of 2020, hydrogen energy is listed as an energy category, which is the first legally confirmed in China that hydrogen energy belongs to energy, at present, hydrogen is taken as clean energy for research and application, hydrogen fuel cell vehicles are more and more popular to enter various fields, and one of the core problems of the hydrogen energy in the use process is as follows: how to guarantee the safety in the aspects of hydrogen use, storage and the like, so that timely and rapid discovery of hydrogen leakage becomes an important part.
The conventional hydrogen leakage detection mode comprises a conventional hydrogen sensor, a portable detection type leak detector, a portable sound wave leak detector, soapy water and the like, but has certain limitations, and the problems of time blind zones, large workload, inconsistent color standard judgment and the like existing in manual inspection exist, for example, the conventional hydrogen sensor is a point distribution type product, and a leakage signal is sent out after monitoring hydrogen in air, so that the conventional hydrogen sensor is expensive, can only be installed in a point distribution type, has many monitoring blind zones, and cannot find leakage points instantly; the portable detection type leak detector has high portability and low price, but has low detection efficiency and needs manual use; the portable sound wave leak detector is easily interfered by other sounds, cannot detect slight leakage, needs manual use and has low efficiency; the soap water can detect a fine leakage point, but the use is inconvenient, and potential safety hazards exist when the soap water is used in a scene with electrical equipment.
Disclosure of Invention
The invention aims to provide an optical fiber hydrogen sensor, a preparation method and a hydrogen leakage detection device.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides an optical fiber hydrogen-sensitive sensor which comprises an optical fiber sensor and a hydrogen-sensitive film coated on an optical fiber sensing area of the optical fiber sensor, wherein the raw material formula of the hydrogen-sensitive film comprises a hydrogen-sensitive material and a binder, the binder comprises polyacrylic acid, and the hydrogen-sensitive material is one or a combination of more of a titanium dioxide hydrogen-sensitive material and a tungsten trioxide hydrogen-sensitive material;
the titanium dioxide hydrogen-sensitive material comprises tetrabutyl titanate and PdCl2Said tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1; the tungsten trioxide hydrogen sensitive material comprises WO3And lanthanum nitrate, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40.
Further, the adhesive also comprises silicon rubber, the silicon rubber comprises one or more of methyl silicon rubber, methyl vinyl silicon rubber and methyl phenyl vinyl silicon rubber, and the mass ratio of the polyacrylic acid to the silicon rubber is 1.5-3: 1.
further, the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
10-20% of hydrogen sensitive material;
80-90% of binder.
Further, the raw material formula of the hydrogen sensitive membrane also comprises a coupling agent, and the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
10-20% of hydrogen sensitive material;
76-86% of a binder;
2-4% of a coupling agent.
Further, the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
further, the titanium dioxide hydrogen-sensitive material is prepared by the following method, which comprises the following steps:
step 1, material preparation: weighing tetrabutyl titanate and PdCl2Tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1;
Further, the tungsten trioxide hydrogen sensitive material is prepared by a reduced pressure distillation method and a heating evaporation method, and comprises the following steps:
(1) preparing a lanthanum-doped tungsten trioxide hydrogen sensitive material by a reduced pressure distillation method: weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, the weighed WO3Dissolving in concentrated hot sodium hydroxide, adding anhydrous ethanol, heating and stirring until the upper layer liquid is yellow and the lower layer liquid is colorless and transparent; adding the upper layer liquid into a round-bottom flask, and distilling under reduced pressure for 4-6 hours; then adding weighed lanthanum nitrate into the flask, continuing to react to uniformly disperse lanthanum ions, and drying in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material;
(2) preparing a lanthanum-doped tungsten trioxide hydrogen sensitive material by a heating evaporation method: weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, useWO to be weighed3Dissolving in concentrated hot sodium hydroxide, adding anhydrous ethanol, and stirring; slowly adding concentrated hydrochloric acid until yellow tungstic acid is generated, stirring and heating, and evaporating the liquid to agglutinate the tungstic acid; and finally, adding lanthanum nitrate to uniformly disperse the lanthanum nitrate, and drying the lanthanum nitrate in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material.
Further, the coupling agent is one or a combination of silane coupling agent and titanate coupling agent.
The invention also provides a preparation method of the optical fiber hydrogen sensor, which comprises the following steps:
s1, the preparation method of the hydrogen sensitive membrane comprises the following steps: according to the formula, the hydrogen sensitive material, the binder and the coupling agent are put into an internal mixer, the mixture is obtained after the materials are mixed and dispersed evenly under normal temperature, and then the mixture is put into a forming machine to obtain the hydrogen sensitive membrane;
s2, coating the hydrogen sensitive film prepared in the step S1 on an optical fiber sensing area of the optical fiber sensor to obtain the optical fiber hydrogen sensitive sensor.
The invention also provides a hydrogen leakage detection device, which comprises the optical fiber hydrogen sensor, a processor and a monitoring system.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the hydrogen sensitive film and the optical fiber micromachining technology are deeply fused to manufacture the flexible optical fiber hydrogen sensitive sensor, and a software monitoring system is developed so as to realize the real-time monitoring of hydrogen leakage, thereby meeting the requirements of different users on manual inspection and real-time online monitoring, and solving the problems of more dead zones of local area detection, untimely leakage finding, large workload of manual inspection and the like existing in the existing hydrogen leakage detection;
the optical fiber hydrogen sensor provided by the invention has the following functional characteristics: softness and self-adhesiveness: the multi-scene full-coverage use requirements can be met, such as pipeline joints, and 360-degree full-coverage monitoring can be realized; optical signal conduction: the hydrogen leakage monitoring system is safe in nature and strong in anti-interference capability, can monitor the hydrogen leakage condition in real time, and can quickly and accurately position a hydrogen leakage point; consumable property: the core part of the flexible optical fiber hydrogen sensor is a consumable part, and through scientific and reasonable product design, the reliable performance of the product is fully ensured, and the market scale of the product is also ensured; the cost advantage is as follows: the preparation cost of the hydrogen sensitive material is greatly reduced, so that the flexible sensor can meet the requirements of a larger area full-coverage monitoring scene.
The hydrogen sensitive material has high color change sensitivity, obvious color change contrast and stable weather resistance under the normal room temperature environment; the optical fiber sensor is intrinsically safe, high in response sensitivity, strong in anti-interference capability and stable in performance; the flexible optical fiber hydrogen sensor is applied to multiple scenes, is full-covered, has no blind area, monitors in real time, finds accurate leakage points in real time, and has stable performance and strong anti-interference capability.
The invention designs the optical fiber hydrogen sensor around the hydrogen sensitive material and the optical fiber sensor, meets different requirements of customers on manual detection and online real-time monitoring, solves the problems of more detection blind areas in local areas, untimely leakage finding, large workload of manual inspection and the like of the existing hydrogen leakage detection, and forms obvious competitive advantages by a one-stop product solution.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of the operation of a fiber optic hydrogen sensor provided by an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a mach-zehnder interference type photonic crystal fiber sensor according to an embodiment of the present invention.
Wherein the reference numerals include: 1-collapse region, 2-air holes around the fiber core of the photonic crystal fiber, 3-cladding of the single-mode fiber, and 4-fiber core.
Detailed Description
The invention will be further described with reference to the examples shown below.
The invention provides an optical fiber hydrogen sensor, which comprises an optical fiber sensor and a hydrogen sensitive film coated on an optical fiber sensing area of the optical fiber sensor.
The raw material formula of the hydrogen sensitive film comprises a hydrogen sensitive material and a binder, wherein the hydrogen sensitive material is one or a combination of more of a titanium dioxide hydrogen sensitive material and a tungsten trioxide hydrogen sensitive material, and the binder comprises polyacrylic acid; the titanium dioxide hydrogen-sensitive material comprises tetrabutyl titanate and PdCl2Said tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1; the tungsten trioxide hydrogen sensitive material comprises WO3And lanthanum nitrate, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40.
The adhesive also comprises silicon rubber, the silicon rubber comprises one or more of methyl silicon rubber, methyl vinyl silicon rubber and methyl phenyl vinyl silicon rubber, and the mass ratio of the polyacrylic acid to the silicon rubber is (1.5-3): 1.
in one embodiment provided by the invention, the raw material formula of the hydrogen sensitive membrane comprises the following components:
10-20% of hydrogen sensitive material;
80-90% of binder.
In a preferred embodiment provided by the present invention, the raw material formulation of the hydrogen sensitive membrane further comprises a coupling agent, and the raw material formulation of the hydrogen sensitive membrane comprises the following components by weight:
10-20% of hydrogen sensitive material;
76-86% of a binder;
2-4% of a coupling agent.
The adhesive comprises polyacrylic acid and silicon rubber, and the raw material formula of the hydrogen sensitive membrane comprises the following components:
in one embodiment provided by the present invention, the titanium dioxide hydrogen-sensitive material is prepared by the following method:
step 1, material preparation: weighing a certain amount of tetrabutyl titanate and PdCl by using an analytical balance2Tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200:1, and tetrabutyl titanate and PdCl2Is preferably 200:1, wherein PdCl2Preferably 2% of the total weight of the final titanium dioxide hydrogen sensitive material;
in another embodiment provided by the present invention, a lanthanum-doped tungsten trioxide hydrogen-sensitive material is prepared by a reduced pressure distillation method, comprising the following steps:
weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, the weighed WO3Dissolving in concentrated sodium hydroxide, adding 50ml anhydrous ethanol, stirring and heating (heating temperature is set to 100-200 deg.C, preferably 150 deg.C) until the upper layer liquid is yellow and the lower layer liquid is colorless and transparent; and adding the upper layer liquid into a round-bottom flask, distilling under reduced pressure for 4-6 hours (preferably 5 hours), adding weighed lanthanum nitrate into the flask, continuing to react to uniformly disperse lanthanum ions, and drying in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material.
In one embodiment provided by the invention, when the lanthanum-doped tungsten trioxide hydrogen-sensitive material is prepared by adopting a reduced pressure distillation method, weighingWO3And lanthanum nitrate in which the molar ratio of lanthanum to W is 1:100, 1:40 or 1: 50.
In still another embodiment provided by the present invention, a lanthanum-doped tungsten trioxide hydrogen-sensitive material is prepared by a heating evaporation method, comprising the following steps:
weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, the weighed WO3Dissolving in concentrated hot sodium hydroxide, adding 50ml of anhydrous ethanol, and stirring uniformly; slowly adding concentrated hydrochloric acid into the beaker until yellow tungstic acid is generated in the beaker, stirring and heating, and evaporating a large amount of liquid to agglutinate the tungstic acid; and finally, adding lanthanum nitrate to uniformly disperse the lanthanum nitrate, and drying the lanthanum nitrate in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material.
In one embodiment provided by the invention, when the lanthanum-doped tungsten trioxide hydrogen-sensitive material is prepared by a heating evaporation method, the weighed WO is3And lanthanum nitrate in which the molar ratio of lanthanum to W is 1:100, 1:40 or 1: 50.
The invention also provides a preparation method of the hydrogen sensitive membrane, which comprises the following steps: according to the formula, the hydrogen sensitive material, the binder and the coupling agent are placed into an internal mixer, the mixture is obtained by stirring the materials at normal temperature until the materials are uniformly mixed and dispersed, and then the mixture is placed into a forming machine to obtain the hydrogen sensitive membrane.
Example 1
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
15% of titanium dioxide hydrogen sensitive material;
and 85% of a binder.
Example 2
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
15% of tungsten trioxide hydrogen sensitive material;
and 85% of a binder.
Example 3
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
15% of titanium dioxide hydrogen sensitive material;
polyacrylic acid 82%;
3% of coupling agent.
Example 4
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 5
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 6
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 7
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 8
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 9
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
example 10
The raw material formulation of the hydrogen sensing membrane provided in this example is shown in table 1, wherein,
comparative example 1
The formula of the raw materials of the hydrogen sensing membrane provided in this example is shown in table 1, which is different from that of example 1,
15% of molybdenum oxide and palladium-gold catalyst;
85% of silicon rubber.
TABLE 1 composition tables for examples 1 to 10 described above
The influence of a titanium dioxide hydrogen sensitive material or a tungsten trioxide hydrogen sensitive material on the performance of the obtained hydrogen sensitive film is examined in the embodiments 1-2 and 4-9;
examples 1 and 3 examined the effect of the addition or non-addition of a silane coupling agent on the performance of the resulting hydrogen-sensitive membrane;
examples 3 and 4 examined the effect of the addition or non-addition of silicone rubber on the performance of the resulting hydrogen-sensitive membrane;
examples 4 and 10 examined the effect of different contents of polyacrylic acid and silicone rubber on the performance of the resulting hydrogen-sensitive membrane.
Comparative test and analysis of test results
First, color change test
The test procedure was as follows: after the hydrogen-sensitive materials obtained in examples 1 to 10 were ground into powders with a mortar, the hydrogen discoloration properties were tested, and the color change and response time of the hydrogen-sensitive film were observed and recorded:
test one: pressing a part of powder on a clean glass plate into a thin sheet, blowing hydrogen on the surface of the thin sheet, and observing the color change performance, wherein the white thin film on the glass plate is light and crisp; the hydrogen gas passing does not change color.
And (2) test II: the other part of the powder was put into a test tube and directly observed for discoloration. And adding a mixture of hydrochloric acid and zinc powder into a beaker, introducing hydrogen generated by reaction into a test tube, and observing the discoloration condition.
In examples 1 to 10, it was found that the powder in the test tube turned blue and a discoloration phenomenon occurred.
Second, adhesive Property test
The test procedure was as follows: the hydrogen-sensitive films obtained in examples 1 to 10 were subjected to adhesion test, the adhesion of the tape was tested using an intelligent electronic tensile tester, the surface of the stainless steel plate was wiped with acetone for 4 times, and the film was left to air for 10 min. The cutter cut out a specimen having a width of 10mm and a length of 100mm from the tape sample. And folding the adhesive surface at one end of the cut sample in half, adhering the other end of the sample to one end of a steel plate, and rolling twice by using a rolling machine at the speed of 600 mm/min. Approximately 20mm of adhesive tape was peeled from the steel plate at the folded end of the sample and the end steel plate and the free end of the sample were clamped in the upper and lower clamps of the apparatus, respectively. And setting parameter information such as test speed (200mm/min), sample width (10mm) and the like, testing, automatically recording the force value in the stripping process by equipment, and reporting the adhesive property of the sample according to the force value, wherein the tensile strength represents the adhesive property (namely the stripping strength).
The test results are shown in table 2 below:
TABLE 2 test results of examples 1-10 and comparative example 1
| Test items | Time to change color(s) | Tensile strength (N/cm) |
| Example 1 | 30 | 3.12 |
| Example 2 | 55 | 3.27 |
| Example 3 | 29 | 3.30 |
| Example 4 | 30 | 2.71 |
| Example 5 | 50 | 2.63 |
| Example 6 | 28 | 2.55 |
| Example 7 | 45 | 2.57 |
| Example 8 | 35 | 2.46 |
| Example 9 | 25 | 2.45 |
| Example 10 | 34 | 2.34 |
| Comparative example 1 | 45 | 2.41 |
And (3) test results:
through embodiments 1-2, it can be derived that: the titanium dioxide hydrogen sensitive material has shorter color change time and quicker reaction than the tungsten trioxide hydrogen sensitive material;
by way of examples 4 to 9, it can be concluded that: after the titanium dioxide hydrogen sensitive material and the tungsten trioxide hydrogen sensitive material are compounded, compared with the tungsten trioxide hydrogen sensitive material, the discoloration time of the compound film is obviously shortened, and the independent titanium dioxide hydrogen sensitive material is improved to a certain extent;
by way of examples 1 and 3, it can be concluded that: the addition of the silane coupling agent has no influence on the color change performance of the hydrogen sensitive film, and has certain improvement effect on the peel strength of the adhesive tape;
by way of examples 3 and 4, it can be concluded that: the addition of the silicon rubber has no influence on the color change time of the hydrogen sensitive film, but the peel strength is reduced;
from examples 4 and 10, it can be concluded that: the different contents of polyacrylic acid and silicon rubber have no influence on the discoloration time of the obtained hydrogen sensitive membrane), and the peel strength is gradually reduced along with the increase of the content of the silicon rubber.
From example 1 and comparative example 1, it can be concluded that: the hydrogen sensitive film prepared in the embodiment 1 has the advantages of shorter color change time, quicker reaction, higher peel strength, low cost of the titanium dioxide hydrogen sensitive material, high cost of the molybdenum oxide and the palladium gold catalyst and greatly reduced production cost.
Compared with silicon rubber, polyacrylic acid has the advantages of hydrophilicity, environmental protection, good air permeability, low cost and the like.
Third, testing of spectral drift data
The hydrogen sensitive film provided in embodiment 9 of the present invention is coated on the optical fiber sensing area of the optical fiber sensor to obtain the optical fiber hydrogen sensitive sensor, the optical fiber hydrogen sensitive sensor is placed at the monitoring point, and hydrogen with known concentration is released to calculate the spectrum drift data of the photonic crystal fiber, see table 3.
Table 3 spectral shift data of the optical fiber hydrogen sensor provided in example 9 of the present invention
| Item | Spectral drift data (pm/RIU) before introducing hydrogen | Spectral shift data (pm/RIU) after introduction of Hydrogen gas |
| Example 9 | 0 | 1118 |
The test shows that the hydrogen sensitive film changes in color and refractive index after encountering hydrogen, so that the spectral drift data of the optical fiber sensor changes, and the leakage of the environmental hydrogen can be monitored in real time by monitoring the spectral drift data of the optical fiber hydrogen sensitive sensor.
For titanium dioxide hydrogen sensitive materials, PdCl is selected2As doping substance, the doping amount is 2% (PdCl)22% of the total weight of the hydrogen sensitive material). Through the color change performance test of the material, the prepared titanium dioxide hydrogen sensitive material has good response time and better color change contrast.
For a tungsten trioxide hydrogen sensitive material, the use amount of noble metals (usually palladium and platinum) can be reduced by doping lanthanum through a heating evaporation process and a reduced pressure distillation process, two materials with the lanthanum-tungsten molar ratio of 1:40 and 1:100 are prepared, the discoloration performance of the materials is tested, and the result shows that the material with the lanthanum-tungsten molar ratio of 1:40 has better response time and good discoloration contrast.
The hydrogen sensitive film prepared by the invention has flexibility and self-adhesiveness, can meet the use requirement of multi-scene full coverage, such as pipeline joint, and can be monitored in 360-degree full coverage; the hydrogen sensitive film is coated on the surfaces of the hydrogen storage transportation pipeline, the hydrogen using equipment and the hydrogen storage equipment or at the interface, so that the method for finding the leakage point is simpler and more convenient, and can be more easily used for monitoring the hydrogen leakage; the hydrogen sensitive film has high color change sensitivity, good color change performance, obvious color change contrast, high response speed and stable weather resistance under the normal room temperature environment; the hydrogen sensitive film can improve the detection efficiency of hydrogen leakage, thereby promoting the use of hydrogen, reducing the combustion of fossil fuel, not only saving the resource which is gradually exhausted, but also helping to solve the global greenhouse effect and the ozone layer hole at present.
The preparation method of the hydrogen sensitive membrane prepared by the invention is simple, the use amount of noble metal is reduced, the cost of materials is reduced, and the energy is saved.
According to the hydrogen sensitive film prepared by the invention, the tungsten trioxide hydrogen sensitive material is prepared by doping rare earth, palladium, platinum and other noble metals, and the color change performance of the tungsten trioxide hydrogen sensitive material can be obviously improved. By testing the response time of the doped tungsten trioxide powder, the following results are found: the sensitivity of the rare earth, palladium and platinum doped tungsten trioxide powder or the film to hydrogen is higher than that of undoped powder, the undoped powder hardly changes at room temperature, the lanthanum and palladium doped powder has shorter response time and larger color change area compared with the platinum doped powder, the color change area of the lanthanum and palladium doped powder is flaky, the powder almost meeting hydrogen can be changed into bluish black, but the platinum doped powder has point color change, and the platinum doped powder has normal temperature recovery property, but the required time is slightly longer.
The optical fiber hydrogen sensitive sensor: the design of the optical fiber sensitive area and the response capability and sensitivity of the sensor are studied as follows:
the sensor is made based on optical fiber and spectral analysis techniques. The hydrogen gas is sent to the sensitive probe through the optical fiber, when the hydrogen gas reacts with the hydrogen sensitive film coated on the optical fiber, the change of the optical characteristics of the light such as intensity, wavelength, phase and the like is caused, the modulated signal is sent to the optical spectrum analyzer through the optical fiber, and the content of the hydrogen gas is measured by analyzing and processing according to the optical characteristics. The working principle of the sensor is shown in figure 1, and the sensing area (optical fiber micro area) is an optical fiber sensor coated with a hydrogen sensitive film, and determines the selectivity, the sensitivity and the response time of the sensor.
The method comprises the following steps of taking a single-mode micro-nano optical fiber as a sensing structure unit, and regulating and controlling the total optical field distribution of a fiber core and a cladding of the optical fiber through optical fiber micromachining technologies such as coning, welding, bending, F-P cavity structures and the like; analyzing the spectral characteristics of the micro-nano optical fiber by using an optical fiber spectrometer to obtain the influence rule of the optical fiber detection arm on the long fiber characteristic interference spectrum; and the single-mode micro-nano structure optical fiber is combined with multi-mode, few-mode, thin core and photonic crystal optical fiber, so that the sensing characteristic parameters are optimized.
The Mach-Zehnder interference type photonic crystal fiber sensor is composed of a photonic crystal fiber and a single-mode fiber SM-28e, namely the sensor is realized by using a mode that an optical fiber welding machine welds a section of photonic crystal fiber in a collapsing mode between two sections of single-mode fibers, as shown in the following figure 2, wherein 1 is a collapsing area in the welding process, 4 is a fiber core, 3 is a cladding, 2 is air holes around the fiber core of the photonic crystal fiber, and an arrow is an optical transmission line.
The collapse region formed in the fusion process of the photonic crystal fiber and the single-mode fiber is used as an excitation region, when light passes through the first collapse region, a part of light enters the cladding from the fiber core, the light is transmitted in the fiber core and the cladding of the photonic crystal fiber together, and finally when the light passes through the second collapse region, the light of the two modes is coupled into the single-mode fiber, so that Mach-Zehnder interference is realized. Compared with the common Mach-Zehnder interference type photonic crystal fiber sensor, the optical fiber hydrogen sensor provided by the invention fully utilizes the photonic crystal fiber and the optical field mode excited by the fusion collapse structure, is favorable for being combined with the later hydrogen sensitive film coating process, and realizes the real-time monitoring of hydrogen.
The refractive index is an important parameter for detection in the environment, and according to the actual parameters of the photonic crystal fiber, as shown in the following table, a photonic crystal fiber sensor model is established and the cross section distribution characteristics of the photonic crystal fiber are researched. The effective refractive index of the photonic crystal fiber with the air hole structure is calculated to be 1.451, and the data is matched with the LMA-10 type photonic crystal fiber.
TABLE 4 specific parameter table for photonic crystal fiber
| Item | LMA-10 type photonic crystal fiber |
| Core diameter/. mu.m | 10.6 |
| Cladding diameter/mum | 120 |
| Refractive index of core | 1.4556 |
| Refractive index of cladding | 1.4541 |
| Pore diameter/. mu.m | 3.026 |
| Pore spacing/. mu.m | 6.757 |
The optical fiber hydrogen sensor provided by the invention utilizes an optical fiber micromachining technology (such as dislocation welding, single-mode-multi-mode-single-mode welding and D-type optical fiber), partial light excites an evanescent field when light passes through an optical fiber micro-region, the region is coated with a selective hydrogen sensitive film, the hydrogen sensitive film changes color and refractive index after encountering hydrogen to cause spectral drift data, and the concentration of the environmental hydrogen can be detected in real time by monitoring the change of optical signals.
The optical fiber hydrogen sensor provided by the invention has the following functional characteristics:
1) softness and self-adhesiveness: the multi-scene full-coverage use requirements can be met, such as pipeline joints, and 360-degree full-coverage monitoring can be realized;
2) optical signal conduction: the hydrogen leakage monitoring system is safe in nature and strong in anti-interference capability, can monitor the hydrogen leakage condition in real time, and can quickly and accurately position a hydrogen leakage point;
3) consumable property: the core part of the flexible optical fiber hydrogen sensor is a consumable part, and through scientific and reasonable product design, the reliable performance of the product is fully ensured, and the market scale of the product is also ensured;
4) the cost advantage is as follows: the preparation cost of the hydrogen sensitive material is greatly reduced, so that the flexible sensor can meet the requirements of a larger area full-coverage monitoring scene.
The optical fiber hydrogen sensor provided by the invention has the advantages that the hydrogen sensitive material has high color change sensitivity and obvious color change contrast, and the weather resistance is stable under the normal room temperature environment; by adopting the hydrogen sensitive material compounding and doping technology, the comprehensive performance of the hydrogen sensitive material is improved, and the preparation cost of the material is greatly reduced; the optical fiber sensor is intrinsically safe, high in response sensitivity, strong in anti-interference capability and stable in performance; the flexible optical fiber hydrogen sensor is applied to multiple scenes, is fully covered, has no blind area, monitors in real time, finds accurate leakage points in real time, and has stable performance and strong anti-interference capability; the fiber microprocessing technology is characterized in that a sensitive and reliable fiber hydrogen sensor is manufactured by processing technologies such as dislocation welding, single-mode-multi-mode-single-mode welding and the like.
The hydrogen sensitive material and the optical fiber sensor are surrounded, the hydrogen sensitive film and the optical fiber micro-processing technology are deeply fused to manufacture the flexible optical fiber hydrogen sensitive sensor, and a software monitoring system is developed to realize the real-time monitoring of hydrogen leakage, so that the requirements of different users on manual inspection and real-time online monitoring are met, the problems that the existing hydrogen leakage detection has many dead zone detection in local areas, untimely leakage detection, large workload of manual inspection and the like are solved, and a one-stop product solution constitutes an obvious competitive advantage.
The invention also provides a preparation method of the optical fiber hydrogen sensor, which comprises the following steps:
s1, the preparation method of the hydrogen sensitive membrane comprises the following steps: according to the formula, the hydrogen sensitive material, the binder and the coupling agent are put into an internal mixer, the mixture is obtained after the materials are mixed and dispersed evenly under normal temperature, and then the mixture is put into a forming machine to obtain the hydrogen sensitive membrane;
s2, coating the hydrogen sensitive film prepared in the step S1 on an optical fiber sensing area of the optical fiber sensor to obtain the optical fiber hydrogen sensitive sensor.
The invention also provides a hydrogen leakage detection device, which comprises the optical fiber hydrogen sensitive sensor, a processor (data processor) and a monitoring system, which jointly form a full-coverage online hydrogen leakage monitoring system, so as to provide an integral solution for hydrogen leakage detection for customers, and the product is mainly applied to hydrogen leakage detection and monitoring in hydrogen production, storage, transportation and use.
The above embodiments are merely illustrative of the technical ideas 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, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. An optical fiber hydrogen sensor, comprising: comprises an optical fiber sensor and a hydrogen sensitive film coated on an optical fiber sensing area of the optical fiber sensor,
the raw material formula of the hydrogen sensitive film comprises a hydrogen sensitive material and a binder, wherein the binder comprises polyacrylic acid, and the hydrogen sensitive material is one or a combination of more of a titanium dioxide hydrogen sensitive material and a tungsten trioxide hydrogen sensitive material;
the titanium dioxide hydrogen-sensitive material comprises tetrabutyl titanate and PdCl2Said tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1;
the tungsten trioxide hydrogen sensitive material comprises WO3And lanthanum nitrate, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40.
2. The fiber optic hydrogen sensor of claim 1, wherein: the adhesive also comprises silicon rubber, the silicon rubber comprises one or more of methyl silicon rubber, methyl vinyl silicon rubber and methyl phenyl vinyl silicon rubber, and the mass ratio of the polyacrylic acid to the silicon rubber is (1.5-3): 1.
3. the fiber optic hydrogen sensor according to claim 1 or 2, wherein: the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
10-20% of hydrogen sensitive material;
80-90% of binder.
4. The fiber optic hydrogen sensor of claim 2, wherein: the raw material formula of the hydrogen sensitive membrane also comprises a coupling agent, and the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
10-20% of hydrogen sensitive material;
76-86% of a binder;
2-4% of a coupling agent.
5. The fiber optic hydrogen sensor of claim 4, wherein: the raw material formula of the hydrogen sensitive membrane comprises the following components in percentage by weight:
6. the fiber optic hydrogen sensor of claim 1, wherein: the titanium dioxide hydrogen-sensitive material is prepared by the following method, and comprises the following steps:
step 1, material preparation: weighing tetrabutyl titanate and PdCl2Tetrabutyl titanate and PdCl2The mass ratio of (1) to (2) is 190-200: 1;
step 2, preparing a mixture: firstly, adding ethylene glycol monomethyl ether into a beaker, and sequentially adding tetrabutyl titanate and PdCl in the step 12Stirring the solution to dissolve the solution, adding deionized water, adding a sodium hydroxide dilute solution, monitoring the pH value of the solution in real time, and adding dilute hydrochloric acid until the pH value of the mixture suspension reaches 7-8 when the solution is completely hydrolyzed when the pH value reaches 10-11;
step 3, heat treatment: placing the mixed suspension with the pH value of 7-8 in the step 2 into an autoclave for heating, wherein the heating temperature range is set to be 100-150 ℃, and the heating time is set to be 60-600 minutes; after heating for a preset time, centrifugally filtering and vacuum drying the suspension to obtain the titanium dioxide hydrogen sensitive material.
7. The fiber optic hydrogen sensor of claim 1, wherein: the tungsten trioxide hydrogen sensitive material is prepared by a reduced pressure distillation method and a heating evaporation method, and comprises the following steps:
(1) preparing a lanthanum-doped tungsten trioxide hydrogen sensitive material by a reduced pressure distillation method: weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, the weighed WO3Dissolving in concentrated hot sodium hydroxide, adding anhydrous ethanol, heating and stirring until the upper layer liquid is yellow and the lower layer liquid is colorless and transparent; adding the upper layer liquid into a round-bottom flask, and distilling under reduced pressure for 4-6 hours; then adding weighed lanthanum nitrate into the flask, continuing to react to uniformly disperse lanthanum ions, and drying in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material;
(2) preparing a lanthanum-doped tungsten trioxide hydrogen sensitive material by a heating evaporation method: weighing WO3And lanthanum nitrate for standby, wherein the molar ratio of lanthanum to W is in the range of 1:100 to 1: 40; firstly, the weighed WO3Dissolving in concentrated hot sodium hydroxide, adding anhydrous ethanol, and stirring; slowly adding concentrated hydrochloric acid until yellow tungstic acid is generated, stirring and heating, and evaporating the liquid to agglutinate the tungstic acid; and finally, adding lanthanum nitrate to uniformly disperse the lanthanum nitrate, and drying the lanthanum nitrate in vacuum to obtain the lanthanum-doped tungsten trioxide hydrogen sensitive material.
8. The fiber optic hydrogen sensor of claim 4, wherein: the coupling agent is one or a combination of more of silane coupling agent and titanate coupling agent.
9. A method of making a fiber optic hydrogen sensor according to any one of claims 1-8, wherein: the method comprises the following steps:
s1, the preparation method of the hydrogen sensitive membrane comprises the following steps: according to the formula, the hydrogen sensitive material, the binder and the coupling agent are put into an internal mixer, the mixture is obtained after the materials are mixed and dispersed evenly under normal temperature, and then the mixture is put into a forming machine to obtain the hydrogen sensitive membrane;
s2, coating the hydrogen sensitive film prepared in the step S1 on an optical fiber sensing area of the optical fiber sensor to obtain the optical fiber hydrogen sensitive sensor.
10. A hydrogen leakage detection device, characterized in that: comprising a fibre-optic hydrogen sensitive sensor according to any of claims 1-8, a processor and a monitoring system.
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| CN111392776A (en) * | 2020-04-03 | 2020-07-10 | 苏州泛氢新材料科技有限公司 | Preparation process of lanthanum-doped tungsten trioxide hydrogen sensitive material |
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