CN104897642B - The detection device of chlorine content in chlorine and chlorine dioxide based on Raman spectrum - Google Patents
The detection device of chlorine content in chlorine and chlorine dioxide based on Raman spectrum Download PDFInfo
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- CN104897642B CN104897642B CN201510250433.7A CN201510250433A CN104897642B CN 104897642 B CN104897642 B CN 104897642B CN 201510250433 A CN201510250433 A CN 201510250433A CN 104897642 B CN104897642 B CN 104897642B
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Abstract
The chlorine content detection device based on Raman spectrum that the invention discloses a kind of, the detection device realize the detection of chlorine content according to the Raman line intensity and its ratio of chlorine in the Raman line intensity or mixed gas of pure chlorine to be measured and other gases.Relative to traditional chemical detection means, chlorine content detection device is based on Raman spectrum, has safer, easier, faster advantage.Meanwhile in structure, since chlorine content detection device collects lateral Raman scattered beam, realizes that exciting light light path and the non co axial of Raman diffused light light path design, the interference of ambient noise can be reduced, there is higher accuracy of detection；The quantity of sense channel can neatly be increased and decreased according to the Raman line characteristic distributions of mixed gas to be measured, there is higher versatility.
Description
Technical field
The present invention relates to spectrometric instrument technical field more particularly to a kind of chlorine and titanium dioxide based on Raman spectrum
The detection device of chlorine content in chlorine.
Background technology
Chlorine (Cl2) it is a kind of yellow green, penetrating odor, poisonous gas, made extensively in chemical industry production
With according to statistics, the chemicals for being more than 60% uses chlorine during its manufacturing, such as chloro-carbon solvent, pesticide, disinfection
Agent, refrigerant, dyestuff, plastics etc..However, with Chemical Manufacture scale continuous enlargement, chlorine leakage accident is in its production, storage
Deposit, transport and use during frequent occurrence, have become the main danger for seriously threatening the country and people's security of the lives and property
One of dangerous chemicals, therefore, it is possible to which safe and simple, rapidly detection chlorine content has great importance.Currently, main logical
Cross the detection that chemical detection means realize chlorine content, wherein iodimetric titration is common detection method, mainly by chlorine to iodine
The oxidation of element is detected.
Chlorine dioxide (ClO2) it is a kind of disinfectant efficiently, safe, it is usually used in drinking water disinfection, however, in titanium dioxide
In the production process of chlorine, chlorine is main reactant, causes to be contaminated with chlorine in product chlorine dioxide, it is therefore desirable to examine
The content for surveying chlorine goes to judge the safety of the transformation efficiency of chlorine dioxide and mixed gas.
In the implementation of the present invention, discovery at least has the following disadvantages in the prior art and deficiency by inventor：
Since chlorine dioxide and chlorine have stronger oxidisability, iodimetric titration to cannot achieve the detection of chlorine content, so,
It needs to find effective chlorine content detection device other than chemical detection means.Existing chlorine content detection device be both needed to
Sample is contacted, and there are some potential safety problemss.
Invention content
The present invention provides the detection device of chlorine content in a kind of chlorine of Raman spectrum and chlorine dioxide, the present invention is real
Show safer, easier, faster chlorine content detection, it is described below：
The detection device of chlorine content, the detection device include in a kind of chlorine and chlorine dioxide of Raman spectrum：Even
Continuous laser, the first optical filter, plane mirror, gas cell, convergent lens, the second optical filter and single-point type detector,
It is provided with window at the top and bottom of the gas cell, at least one window is provided on side wall；It is described to assemble thoroughly
Mirror, second optical filter and the single-point type detector constitute at least one set of sense channel；
The continuous wave laser generates excitation beam, and first optical filter is bandpass filter, for filtering out the company
The stray light of continuous laser itself；
For the plane mirror for excitation beam of transferring, the upper vertical of excitation beam from the gas cell is incident downwards
Into gaseous sample, Raman scattering light beam is inspired at the gas cell；
The sense channel that the convergent lens, second optical filter and the single-point type detector are constituted is for collecting side
To Raman scattering light beam, the non co axial for forming excitation beam and lateral Raman scattered beam designs；Second optical filter is used for
Filter out the excitation beam being mixed in lateral Raman scattered beam and Rayleigh scattering light beam, and limit allow by light beam
Wave-length coverage；
Lateral Raman scattered beam in sense channel is converted into electric signal by the single-point type detector, is obtained Raman and is dissipated
Intensity information is penetrated, the content of chlorine is obtained by the Raman active of Raman scattered light intensity information and gas.
Wherein, the single-point type detector is specially：Photomultiplier or avalanche mode photodiodes.
Wherein, the gas cell and the single-point type detector are in Nonimage Conjugate Relations.
Wherein, the excitation beam is incident in gaseous sample vertically downward from the surface of the gas cell.
The advantageous effect of technical solution provided by the invention is：The present invention according to the Raman line intensity of pure chlorine to be measured or
The Raman line intensity and its ratio of chlorine and other gases realize the detection of chlorine content in mixed gas, relative to tradition
Chemical detection means, have safer, easier, faster advantage；Simultaneously as the optimization of structure of the detecting device, packet
It includes exciting light light path and collects the non co axial design of light path and the on-fixed of sense channel, detection dress with Raman diffused light
It sets and improves accuracy of detection, enhance flexibility and versatility.
Description of the drawings
Fig. 1 is the structural representation of the detection device of chlorine content in a kind of chlorine and chlorine dioxide based on Raman spectrum
Figure；
Fig. 2 is the structural schematic diagram of gas cell.
In attached drawing, parts list represented by the reference numerals are as follows：
1：Continuous wave laser； 2：First optical filter；
3：Plane mirror； 4：Gas cell；
5：Convergent lens； 6：Second optical filter；
7：Single-point type detector； P：Plane；
A：Excitation beam incident window； B：Excitation beam exit window；
C1、C2：For lateral Raman scattered beam detection window； L、L1And L2：Optical axis.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made below further
It is described in detail on ground.
Raman spectrum is based on Raman scattering effect, is irradiated on substance according to exciting light and photon and the friendship of intermolecular energy occurs
The inelastic scattering for changing and generating identifies different material molecule knots for differentiating different material molecule group vibration modes
Structure distinguishes different material molecules.Meanwhile in conjunction with chemometrics method, realizing the Accurate Determining of material component content information,
The target for reaching qualitative analysis and quantitatively detecting.Raman spectrum has significant advantage, including：Sample, non-destructive testing are not contacted,
It is suitble to the detection of black sample and aqueous specimen, it is fast adapts to severe detection environment, the light spectrum image-formings such as high temperature, low temperature and high pressure
Speed, easy, real-time etc., are widely used in medicine and pharmacy, chemistry and material science, Food Science, environmental protection, geology
The fields such as archaeology, criminal investigation identification.
Raman spectrum can be real according to the Raman line intensity of chlorine dioxide and the Raman line intensity and its ratio of chlorine
The detection of existing chlorine dioxide content and chlorine content and its ratio, to effectively judge the transformation efficiency of chlorine dioxide.And
And during acquiring Raman scattering signal, without being contacted with sample, with higher safety, meanwhile, have easier
Operation and the output of faster result.
Embodiment 1
An embodiment of the present invention provides the detection device of chlorine content in a kind of chlorine of Raman spectrum and chlorine dioxide, ginsengs
See Fig. 1, which includes：Continuous wave laser 1, the first optical filter 2, plane mirror 3, gas cell 4, convergent lens 5,
Two optical filters 6 and single-point type detector 7.
Referring to Fig. 2, the top and bottom of gas cell 4 are provided with window, and at least one window is provided on side wall.It assembles saturating
Mirror 5, the second optical filter 6 and single-point type detector 7 constitute at least one set of sense channel.
When practical application, it can increase according to the Raman line characteristic distributions of mixed gas to be measured or reduce detection and lead to
The quantity in road；Number of windows on gas cell side wall can also be set, the embodiment of the present invention is to sense channel and window
Quantity be not limited.
The excitation beam of the generation of continuous wave laser 1 high power, narrow linewidth, the first optical filter 2 is bandpass filter, for filtering
Except the stray light of of continuous wave laser 1 itself.Plane mirror 3 is for transferring excitation beam, and excitation beam is from the top of gas cell 4
(right over preferably) is incident in gaseous sample vertically downward, and Raman scattering light beam is inspired at gas cell 4.Convergent lens 5,
The sense channel that second optical filter 6 and single-point type detector 7 are constituted forms excitation beam for collecting lateral Raman scattered beam
It is designed with the non co axial of lateral Raman scattered beam, inhibits the strong background noise interference based on excitation beam.Second optical filter 6
For filtering out the excitation beam being mixed in lateral Raman scattered beam and Rayleigh scattering light beam, and limit allow by light
The wave-length coverage of beam.
Single-point type detector 7 can use photomultiplier (PMT), avalanche mode photodiodes etc., respectively that detection is logical
Raman scattering light beam in road is converted into electric signal, obtains Raman scattered light intensity information, passes through Raman scattered light intensity information
And the Raman active of gas obtains the content of chlorine.
Embodiment 2
The inspection of chlorine content in the described mainly a kind of chlorine and chlorine dioxide of Raman spectrum of the embodiment of the present invention
Device is surveyed, which realizes chlorine dioxide (ClO2) chlorine (Cl in gas2) content detection.Referring to Fig. 1, the detection
Device includes：Continuous wave laser 1, the first optical filter 2, plane mirror 3, gas cell 4, convergent lens 5,6 and of the second optical filter
Single-point type detector 7.
Convergent lens 5, the second optical filter 6 and single-point type detector 7 constitute 2 groups of sense channels, the respectively first detection
Channel D1With the second sense channel D2.First sense channel D1With the second sense channel D2Differ only in second optical filter 6
Light-filtering characteristic.Optical axis H, optical axis L1And optical axis L2Not in same level, there is different vertical heights, wherein optical axis H's
Vertical height highest.
When practical application, it can increase according to the Raman line characteristic distributions of mixed gas to be measured or reduce detection and lead to
The quantity in road.The embodiment of the present invention is not limited the quantity of sense channel.
Referring to Fig. 2, the top of gas cell 4 is provided with window A, bottom is provided with window B, is provided with window C on left side wall1
With window C2, window A is excitation beam incident window, and window B is excitation beam exit window, window C1With window C2It is side
To Raman scattering light beam detection window, it can increase or reduce inspection according to the Raman line characteristic distributions of mixed gas to be measured
Survey the quantity of window.Window C1With window C2The plane P at place is perpendicular to optical axis L, optical axis L and optical axis L1And optical axis L2It is parallel.
It is the Gao Gong of 532nm, power not less than 50mW, line width no more than 0.6nm that continuous wave laser 1, which generates centre wavelength,
The excitation beam of rate, narrow linewidth.The bandpass filter of wavelength 532nm, halfwidth 1nm centered on first optical filter 2, for filtering out
The stray light of of continuous wave laser 1 itself.The turnover excitation beam of plane mirror 3, makes excitation beam hang down from the surface of gas cell 4
Directly it is incident in gaseous sample downwards.
Excitation beam is incident from window A at gas cell 4, is emitted from window B, and the Raman scattering light beam inspired penetrates window
C1With window C2It is propagated to side, and respectively by by 7 three parts group of convergent lens 5, the second optical filter 6 and single-point type detector
At the first sense channel D1With the second sense channel D2It is detected.2 groups of sense channels mainly collect lateral Raman diffused light
Beam, forms exciting light light beam and the non co axial of lateral Raman scattering light detection light beam designs, and inhibits strong based on excitation beam
Ambient noise interferes.
The Raman line distribution situation of 1 chlorine of table and chlorine dioxide
Wherein, Raman shift and Raman active are the intrinsic characteristic of different material molecular radical, the wave with excitation beam
Length is unrelated；The position of Raman line is codetermined by the wavelength of excitation beam and Raman shift, Raman line N shown in table1、M1、
M2And M3Both correspond to the excitation beam that wavelength is 532nm.
According to the Raman line distribution situation of chlorine shown in table 1 and chlorine dioxide it is found that chlorine only has 546.9nm (N1)
Raman line, chlorine dioxide has 543.9nm (M1)、557.7nm(M2) and 561.5nm (M3) three Raman lines.Due to N1With
M1Wavelength only differs 3nm, M2And M3Wavelength only differs 3.8nm, it is contemplated that the limitation of bandpass filter minimum passing band wavelength range,
By N1And M1It is divided into one group, by M2And M3It is divided into another group, detects the intensity I of lateral Raman scattered beam respectively1And I2.Therefore,
Gas cell 4 needs that window C is arranged1With window C2Constitute sense channel D1With sense channel D2。
In order to collect lateral Raman scattered beam, the window C of gas cell 4 as much as possible1With window C2Respectively by right
The convergent lens 5 of sense channel is answered (to use * tables in Fig. 1 in Nonimage Conjugate Relations with the single-point type detector 7 of corresponding sense channel
Show).
In order to enable the first sense channel D1Only detect N1And M1The intensity of two Raman lines, the first sense channel D1
The second optical filter 6 using centre wavelength 545nm, halfwidth 10nm bandpass filter；
In order to enable the second sense channel D2Only detect M2And M3The intensity of two Raman lines, the second sense channel D2
The second optical filter 6 using centre wavelength 560nm, halfwidth 10nm bandpass filter.
Single-point type detector 7 can use photomultiplier (PMT), avalanche mode photodiodes etc., respectively by the first inspection
Survey channel D1With the second sense channel D2Raman scattering optical signal be converted into electric signal, obtain Raman scattered light intensity information I1
And I2。
According to Raman scattered light intensity information I1And I2And Raman line N1、M1、M2And M3Raman active may infer that
Go out chlorine content (concentration) Z1With chlorine dioxide content (concentration) Z2, wherein k1And k2It is the first sense channel D respectively1With second
Sense channel D2Calibration factor, can be obtained by the detection of standard sample.
To the model of each device in addition to doing specified otherwise, the model of other devices is not limited the embodiment of the present invention,
As long as the device of above-mentioned function can be completed.
It will be appreciated by those skilled in the art that attached drawing is the schematic diagram of a preferred embodiment, the embodiments of the present invention
Serial number is for illustration only, can not represent the quality of embodiment.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (3)
1. the detection device of chlorine content, the detection device include in a kind of chlorine and chlorine dioxide based on Raman spectrum：
Continuous wave laser, the first optical filter, plane mirror, gas cell, convergent lens, the second optical filter and single-point type detector,
It is characterized in that,
It is provided with window at the top and bottom of the gas cell, two windows are provided on side wall；The convergent lens, described
Two optical filters and the single-point type detector constitute two groups of sense channels, and respectively the first sense channel and the second detection are logical
Road；
The continuous wave laser generates excitation beam, and first optical filter is bandpass filter, described continuous sharp for filtering out
The stray light of light device itself；
The plane mirror is incident on downwards gas for excitation beam of transferring, excitation beam from the upper vertical of the gas cell
In body sample, Raman scattering light beam is inspired at the gas cell；
The sense channel that the convergent lens, second optical filter and the single-point type detector are constituted is laterally pulled for collecting
Graceful scattered beam, the non co axial for forming excitation beam and lateral Raman scattered beam design；Second optical filter is for filtering out
The excitation beam and Rayleigh scattering light beam being mixed in lateral Raman scattered beam, and limit allow by light beam wavelength
Range；
Lateral Raman scattered beam in sense channel is converted into electric signal by the single-point type detector, obtains Raman diffused light
Strength information obtains the content of chlorine by the Raman active of Raman scattered light intensity information and gas；
The gas cell and the single-point type detector are in Nonimage Conjugate Relations；The detection device is according to the drawing of pure chlorine to be measured
The Raman line intensity and its ratio of chlorine and chlorine dioxide realize the inspection of chlorine content in graceful the intensity of spectral line or mixed gas
It surveys；
Chlorine has the Raman line of 546.9nm, chlorine dioxide to have tri- Raman lines of 543.9nm, 557.7nm and 561.5nm；
In order to enable the first sense channel only detects that the intensity of two Raman lines of 546.9nm and 543.9nm, the first detection are logical
Second optical filter in road uses the bandpass filter of centre wavelength 545nm, halfwidth 10nm；
In order to enable the second sense channel only detects that the intensity of two Raman lines of 557.7nm and 561.5nm, the second detection are logical
Second optical filter in road uses the bandpass filter of centre wavelength 560nm, halfwidth 10nm；
Wherein, it is specially by the content of the Raman active of Raman scattered light intensity information and gas acquisition chlorine：
According to Raman scattered light intensity information I1And I2And the Raman active of four Raman lines can be inferred that chlorine content Z1
With chlorine dioxide content Z2, wherein k1And k2It is the calibration factor of the first sense channel and the second sense channel respectively, can passes through
The detection of standard sample obtains；
Wherein, N1、M1、M2And M3Respectively Raman line.
2. detection device according to claim 1, which is characterized in that the single-point type detector is specially：Photomultiplier transit
Pipe or avalanche mode photodiodes.
3. detection device according to claim 1, which is characterized in that the excitation beam is from the surface of the gas cell
It is incident in gaseous sample vertically downward.
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| EP3961195A1 (en) * | 2020-08-28 | 2022-03-02 | Siemens Aktiengesellschaft | Measuring device for determining the calorific value of a hydrocarbon-containing fuel gas |
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