CN110849826B - Reaction membrane manufacturing method and ammonia nitrogen detection device and method based on reaction membrane - Google Patents
Reaction membrane manufacturing method and ammonia nitrogen detection device and method based on reaction membrane Download PDFInfo
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- CN110849826B CN110849826B CN202010040845.9A CN202010040845A CN110849826B CN 110849826 B CN110849826 B CN 110849826B CN 202010040845 A CN202010040845 A CN 202010040845A CN 110849826 B CN110849826 B CN 110849826B
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- 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
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Abstract
The invention relates to the technical field of ammonia nitrogen detection, in particular to a manufacturing method of a reaction membrane, and an ammonia nitrogen detection device and method based on the reaction membrane, wherein the manufacturing method of the reaction membrane comprises the following steps: firstly, preparing a polyvinylidene chloride-bromothymol blue solution for coating, and then coating a film on the optical fiber so as to form a reaction film on the surface of the inclined fiber grating cladding; the ammonia nitrogen detection device comprises: the invention also provides a corresponding ammonia nitrogen detection method, which adopts light as a carrier of signals and has the characteristic of high speed. The preparation process of the reaction film is simple and the cost is low. The ammonia nitrogen detection device has a simple structure, does not need a complex sample pool reaction system, and has high detection precision.
Description
Technical Field
The invention relates to the technical field of ammonia nitrogen detection, in particular to a manufacturing method of a reaction membrane, and an ammonia nitrogen detection device and method based on the reaction membrane.
Background
The sewage treatment is a difficult problem facing China at present, along with the increasing and rapid increase of the population, the discharge of domestic sewage and industrial development sewage causes serious pollution to water resources, and one of the common components in the sewage is ammonia nitrogen. The means for accurately and rapidly detecting the ammonia nitrogen concentration in the water solution becomes the necessary requirement for treating sewage.
The traditional measuring means comprises a PH sensor, an ammonia nitrogen sensor and a test paper detection method. The PH sensor and the ammonia nitrogen sensor are common measurement means, but are easily influenced by the surrounding environment, other signal interference is easily doped in signals transmitted back by the sensors to generate signal drift, temperature drift is common, namely the result that whether the change of the signals is temperature change or ammonia nitrogen concentration change is not determined, meanwhile, the traditional method for detecting ammonia nitrogen by using test paper determines the ammonium ion concentration by contrasting a standard colorimetric diagram based on the change of the color of the test paper, the method is not only complex in operation, but also human eyes are not sensitive to tiny change of the color, and accurate judgment is difficult to give.
Disclosure of Invention
In order to solve the problems, the invention provides a manufacturing method of a reaction membrane, and a device and a method for detecting ammonia nitrogen based on the reaction membrane, and aims to at least solve one of the technical problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the method for manufacturing the reaction film provided by the embodiment of the invention comprises the following steps:
(1) preparing a polyvinylidene chloride-bromothymol blue solution for coating: the solute is polyvinylidene chloride and bromothymol blue, the organic solvent is N-methyl pyrrolidone, 0.1g of polyvinylidene chloride and 0.1g of bromothymol blue are taken and put into 5ml of N-methyl pyrrolidone solvent, then the mixture is put on a magnetic control stirrer to work for 6 hours, and after the mixture is fully stirred, a uniform solution is obtained;
(2) coating a film on the optical fiber: vertically suspending and fixing the optical fiber, taking 1ml of the solution prepared in the step (1) by using a rubber head dropper, dropwise adding the solution from the upper part of the optical fiber, allowing the solution to flow downwards under the action of gravity, passing through the surface of the optical fiber in a grid area, standing for 12 hours, and allowing the organic solvent N-methyl pyrrolidone to be fully volatilized to only leave a reaction film consisting of polyvinylidene chloride and bromothymol blue and attached to the surface of the inclined optical fiber grating cladding.
The invention also provides a reaction membrane-based ammonia nitrogen detection device, which comprises: the optical fiber spectrometer comprises a light source, a single-mode optical fiber, an inclined fiber grating, a sample cell and a spectrometer which are sequentially connected through optical fibers, wherein a layer of reaction film is plated on a cladding of the inclined fiber grating, and the reaction film is obtained through the manufacturing method of the reaction film according to claim 1.
Further, the inclination angle of the inclined fiber grating is 18 degrees, and the length of the gate region is 20 mm.
Further, the resolution of the spectrometer was set to 0.1nm, the frequency was set to 200Hz, the sampling point was 2001pt, and the wavelength range was: 1480nm to 1620 nm.
The invention also provides a detection method of ammonia nitrogen concentration, and the ammonia nitrogen detection device comprises the following steps:
(1) the two ends of the inclined fiber grating are respectively connected into a light source and a spectrometer through fiber jumpers, the resolution of the spectrometer is set to be 0.1nm, the frequency is set to be 200Hz, the sampling point is 2001pt, and the wavelength range is as follows: 1480nm to 1620nm, and a spectrogram is called;
(2) and immersing the inclined fiber grating coated with the reaction film into an ammonia nitrogen solution, and starting a spectrometer to automatically collect the change of light energy intensity along with time to obtain the ammonia nitrogen concentration in the ammonia nitrogen solution.
Further, the wavelength of the spectrometer was set to 1516.32 nm.
Further, the spectrometer also records the light energy intensity change information corresponding to the fiber core mode.
The invention has the beneficial effects that: the invention discloses a method for manufacturing a reaction membrane, and a device and a method for detecting ammonia nitrogen based on the reaction membrane, wherein the method for manufacturing the reaction membrane comprises the following steps: firstly, preparing a polyvinylidene chloride-bromothymol blue solution for coating, and then coating a film on the optical fiber so as to form a reaction film on the surface of the inclined fiber grating cladding; the ammonia nitrogen detection device comprises: the invention also provides a corresponding ammonia nitrogen detection method, which adopts light as a carrier of signals and has the characteristic of high speed. The preparation process of the reaction film is simple and the cost is low. The ammonia nitrogen detection device has a simple structure, does not need a complex sample pool reaction system, and has high detection precision.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described 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 without inventive exercise.
FIG. 1 is a schematic structural diagram of a reaction membrane-based ammonia nitrogen detection device, in which: 1. a light source, 2 optical fibers, 3 inclined fiber gratings, 4 a sample cell and 5 a spectrometer;
FIG. 2 is a schematic structural diagram of a tilted fiber grating;
FIG. 3 is a graph of the variation of light energy intensity in calibration mode for an embodiment of the invention;
FIG. 4 is a graph of the variation of the intensity of light energy in a core mode for an embodiment of the present invention;
FIG. 5 is a graph of response rate of light energy intensity over time in calibration mode according to an embodiment of the present invention.
Detailed Description
The conception, specific structure and technical effects of the present disclosure will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present disclosure. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The preparation method of the reaction film provided by the invention comprises the following steps:
(1) preparing a polyvinylidene chloride-bromothymol blue solution for coating: the solute is polyvinylidene chloride and bromothymol blue, the organic solvent is N-methyl pyrrolidone, 0.1g of polyvinylidene chloride and 0.1g of bromothymol blue are taken and put into 5ml of N-methyl pyrrolidone solvent, then the mixture is put on a magnetic control stirrer to work for 6 hours, and after the mixture is fully stirred, a uniform solution is obtained;
(2) coating a film on the optical fiber: vertically suspending and fixing the optical fiber, taking 1ml of the solution prepared in the step (1) by using a rubber head dropper, dropwise adding the solution from the upper part of the optical fiber, allowing the solution to flow downwards under the action of gravity, passing through the surface of the optical fiber in a grid area, standing for 12 hours, and allowing the organic solvent N-methyl pyrrolidone to be fully volatilized to only leave a reaction film consisting of polyvinylidene chloride and bromothymol blue and attached to the surface of the inclined optical fiber grating cladding.
The reaction membrane provided by the embodiment is very simple in preparation process and low in cost, and can generate specific recognition on ammonia nitrogen.
Referring to fig. 1 and 2, the invention also provides a reaction membrane-based ammonia nitrogen detection device, comprising: the optical fiber spectrometer comprises a light source 1, a single-mode fiber 2, an inclined fiber grating 3, a sample cell 4 and a spectrometer 5 which are sequentially connected through optical fibers, wherein a layer of reaction film 6 is plated on a cladding of the inclined fiber grating 3, and the reaction film 6 is obtained through the manufacturing method.
In a preferred embodiment, the inclined angle of the inclined fiber grating 3 is 18 degrees, and the length of the grating region is 20 mm.
In a preferred embodiment, the resolution of the spectrometer 5 is set to 0.1nm, the frequency is set to 200Hz, the sampling point is 2001pt, and the wavelength range is: 1480nm to 1620 nm.
When the device is used, light emitted by the light source 1 enters the spectrometer 5 after passing through the inclined fiber grating 3, and the spectrometer 5 measures the light energy intensity after passing through the inclined fiber grating 3 in real time to obtain a spectrogram.
In the field of optical fiber sensing, the inclined fiber grating 3 forms a grating which forms a certain included angle with the axial direction of an optical fiber in a fiber core by an ultraviolet writing method under the condition of not damaging the structure of the optical fiber, so that hundreds of cladding modes which are very sensitive to the refractive index of the surrounding environment are excited, detection objects are enriched, and the measurement precision is improved. In this embodiment, the tilted fiber grating 3 is written by an excimer laser and a phase mask method. The inclined fiber grating 3 has the characteristics of improving the measurement precision without damaging the optical fiber besides the characteristics of the conventional fiber sensor. Meanwhile, the fiber core mode is only sensitive to temperature and pressure and is insensitive to the external refractive index, so that the refractive index and the temperature can be simultaneously distinguished and measured, and the temperature drift can be effectively monitored and eliminated by detecting the light energy intensity in the fiber core mode.
Compared with the traditional ammonia nitrogen sensor, the device adopts light as a carrier of signals and has the characteristic of high speed. The whole device has simple structure, does not need a complex sample cell reaction system, and has high detection precision.
The invention also provides an ammonia nitrogen concentration detection method based on the ammonia nitrogen detection device, which comprises the following steps:
(1) the two ends of the inclined fiber grating are respectively connected into a light source and a spectrometer through fiber jumpers, the resolution of the spectrometer is set to be 0.1nm, the frequency is set to be 200Hz, the sampling point is 2001pt, and the wavelength range is as follows: 1480nm to 1620nm, and a spectrogram is called;
(2) and immersing the inclined fiber grating coated with the reaction film into an ammonia nitrogen solution, starting a spectrometer to automatically collect the change of light energy intensity along with time, and obtaining the ammonia nitrogen concentration in the ammonia nitrogen solution by detecting the response rate of a calibration mode.
Because the surface of the inclined fiber grating is plated with a layer of reaction film with high refractive index, the cladding mode with the effective refractive index smaller than the refractive index of the reaction film in the cladding mode excited by the inclined fiber grating cannot form total reflection in the fiber cladding, and the energy is gradually coupled into the external environment to form a leakage mode, so that the energy of the partial mode in the spectrum is lower, and the extinction ratio is also lower.
And immersing the inclined fiber grating into an ammonia nitrogen solution to be detected, reacting the ammonia nitrogen with a reaction film on a cladding of the inclined fiber grating, corroding the reaction film, gradually reducing the surface refractive index of the inclined fiber grating along with the corrosion process, and gradually converting the leakage mode into a conduction mode and transmitting the conduction mode in the fiber cladding to form a cladding conduction mode. As the corrosion degree is deepened, more leakage modes are converted into conduction modes of the cladding to be transmitted in the optical fiber, the total energy detected by the spectrometer also presents a rising state, and the extinction ratio of the cladding mode also presents a trend of increasing, namely the upper edge of the cladding mode in the spectrum is in a rising state, the lower edge of the cladding mode in the spectrum is in a falling state, and the rising and falling speeds of the cladding mode are related to the concentration of ammonia nitrogen in the solution.
In a preferred embodiment, the wavelength of the spectrometer is set to 1516.32 nm.
In a preferred embodiment, the spectrometer further records light energy intensity change information corresponding to the fiber core mode, and the light energy intensity change information is used for correcting cross effects caused by external temperature changes in the detection process, so that the measurement accuracy is improved.
To better explain the method for detecting ammonia nitrogen concentration provided by the present invention, referring to fig. 3, fig. 3 is a graph showing the variation of light energy intensity in a calibration mode (wavelength of 1516.32 nm) during the corrosion of a reaction film on the cladding surface of an inclined fiber grating of the apparatus for detecting ammonia nitrogen concentration of the present invention. Fig. 3 shows that the light energy intensity corresponding to the calibration mode gradually decreases as the reaction membrane is gradually corroded by ammonia nitrogen. Therefore, the reaction membrane can generate specific recognition on ammonia nitrogen.
Referring to fig. 4, fig. 4 is a graph showing the variation of the light energy intensity in the fiber core mode during the corrosion of the reaction film on the inclined fiber grating cladding surface of the ammonia nitrogen concentration detection device of the present invention. It can be seen from fig. 4 that in the process of gradually corroding the reaction film with ammonia nitrogen, the fiber core mode has no obvious change to the refractive index and has obvious change to the temperature, and the light energy intensity corresponding to the fiber core mode detected by the spectrometer is basically unchanged, so that the influence of the temperature change on the measurement result in the process is eliminated, and the temperature self-compensation function is realized.
Referring to fig. 5, fig. 5 is a graph of response rate of light energy intensity with time in calibration mode when ammonia nitrogen solutions with different concentrations are measured by the detection method of the present invention. As can be seen from FIG. 5, in the 10mg/L ammonia nitrogen solution, because the ammonia nitrogen concentration is relatively high, the reaction film on the cladding surface of the inclined fiber grating is corroded at the fastest rate, the light energy intensity change rate in the calibration mode is also fastest, and the amplitude of the light energy intensity change is also the largest; in 5mg/L and 1mg/L ammonia nitrogen solutions, the rate of light energy intensity change in the calibration mode is relatively slow, and the amplitude of light energy intensity change is also reduced in sequence; and in the water without ammonia nitrogen, the light energy intensity in the calibration mode is hardly changed.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions as will be apparent to those skilled in the art without departing from the spirit of the invention and its scope is defined by the claims appended hereto.
Claims (6)
1. The manufacturing method of the reaction film is characterized by comprising the following steps:
(1) preparing a polyvinylidene chloride-bromothymol blue solution for coating: the solute is polyvinylidene chloride and bromothymol blue, the organic solvent is N-methyl pyrrolidone, 0.1g of polyvinylidene chloride and 0.1g of bromothymol blue are taken and put into 5ml of N-methyl pyrrolidone solvent, then the mixture is put on a magnetic control stirrer to work for 6 hours, and after the mixture is fully stirred, a uniform solution is obtained;
(2) coating a film on the optical fiber: vertically suspending and fixing the optical fiber, taking 1ml of the solution prepared in the step (1) by using a rubber head dropper, dropwise adding the solution from the upper part of the optical fiber, allowing the solution to flow downwards under the action of gravity, passing through the surface of the optical fiber in a grid area, standing for 12 hours, and allowing an organic solvent N-methyl pyrrolidone to be sufficiently volatilized to leave only a reaction film consisting of polyvinylidene chloride and bromothymol blue and attached to the surface of a cladding layer of the inclined optical fiber grating, wherein the inclination angle of the inclined optical fiber grating is 18 degrees, and the length of the grid area is 20 mm.
2. Ammonia nitrogen detection device based on reaction film, its characterized in that includes: the optical fiber grating spectrometer comprises a light source, an inclined optical fiber grating and a spectrometer which are sequentially connected through a single-mode optical fiber, wherein the inclined optical fiber grating is arranged in a sample cell, a layer of reaction film is plated on a cladding of the inclined optical fiber grating, the inclination angle of the inclined optical fiber grating is 18 degrees, the length of a grid region is 20mm, and the reaction film is obtained through the manufacturing method of the reaction film according to claim 1.
3. The ammonia nitrogen detection device based on the reaction membrane as claimed in claim 2, wherein the resolution of the spectrometer is set to 0.1nm, the frequency is set to 200Hz, the sampling point is 2001pt, and the wavelength range is as follows: 1480nm to 1620 nm.
4. An ammonia nitrogen concentration detection method by using the ammonia nitrogen detection device of any one of claims 2 or 3, which is characterized by comprising the following steps:
(1) the two ends of the inclined fiber grating are respectively connected into a light source and a spectrometer through single-mode fiber jumpers, the resolution of the spectrometer is set to be 0.1nm, the frequency is set to be 200Hz, the sampling point is 2001pt, and the wavelength range is as follows: 1480nm to 1620nm, and a spectrogram is called;
(2) and immersing the inclined fiber grating coated with the reaction film into an ammonia nitrogen solution, and starting a spectrometer to automatically collect the change of light energy intensity along with time to obtain the ammonia nitrogen concentration in the ammonia nitrogen solution.
5. The method for detecting the concentration of ammonia nitrogen as claimed in claim 4, wherein the wavelength of the spectrometer is set to 1516.32 nm.
6. The ammonia nitrogen concentration detection method according to claim 4, wherein the spectrometer further records light energy intensity change information corresponding to the fiber core mode.
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