WO2022083044A1

WO2022083044A1 - Online measurement system and method for particle size distribution of atmospheric particulates

Info

Publication number: WO2022083044A1
Application number: PCT/CN2021/078133
Authority: WO
Inventors: 韩鹏; 黄桂琼; 徐炳权; 彭力; 邱健; 骆开庆; 刘冬梅
Original assignee: 华南师范大学
Priority date: 2020-10-20
Filing date: 2021-02-26
Publication date: 2022-04-28
Also published as: CN112504922B; CN112504922A

Abstract

An online measurement system and method for the particle size distribution of atmospheric particulates. The system comprises a sample collection unit (10), a peristaltic pump (20), a measurement unit (30) and a signal processing unit (40), wherein the measurement unit (30) comprises a sample pool (31), a laser device (32) and a detector (37); the sample collection unit (10) collects an atmospheric sample and converts same into a sample solution; the peristaltic pump (20) injects the sample solution into the sample pool (31) in at least two different speeds, respectively; the laser device (32) emits laser light to the sample pool (31) that contains the sample solution; the detector (37) detects scattered light which is respectively generated when the peristaltic pump (20) injects the sample solution at different speeds, and converts the scattered light into scattered-light electric signals; and the signal processing unit (40) receives different scattered-light electric signals, fits particle size information of atmospheric particulates by combining the different injection speeds of the sample solution, and outputs the particle size information.

Description

An online measurement system and method for particle size distribution of atmospheric particles

technical field

The invention relates to the related research field of atmospheric environment monitoring, in particular to real-time online measurement of particle size distribution of atmospheric particles.

Background technique

With the development of economy and the acceleration of urbanization, atmospheric particulate pollution has become a hot spot of social concern. It is worth noting that the particle size distribution of atmospheric particles is the basis for the source analysis of atmospheric particle pollution and the pathological study of related diseases caused by atmospheric particles.

In recent years, my country's atmospheric particulate matter monitoring technology has made great progress. Among them, the production of PM _2.5 detectors has formed a certain scale. However, most of these instruments use offline methods, and the pre-processing is complicated and time-consuming, resulting in low measurement accuracy, difficulty in real-time measurement, and high price. It is not suitable for large-scale use.

With the advancement of optical technology, dynamic light scattering technology has gradually become one of the mainstream measurement methods of atmospheric particle monitoring instruments due to its non-contact and non-destructive advantages. Companies such as Malvern in the United Kingdom and TSI in the United States have successively launched commercial instruments. However, the measurement of particle size by dynamic light scattering technology is only suitable for systems with only Brownian motion of particles. However, during the online measurement of atmospheric particulate matter, there must be directional movement of the particles when the sample is drawn.

The traditional dynamic light scattering technology to detect the particle size of atmospheric particles includes the following steps:

S1: Collect atmospheric samples containing atmospheric particles and convert them into sample solutions;

S2: inject the sample solution into the sample cell at a certain speed, after the sample solution is stationary in the sample cell, inject laser light into the sample cell to detect the scattered light generated when the sample solution is in the stationary state, and convert it into is the scattered photoelectric signal;

S3: Receive the scattered photoelectric signal generated in step S2, and calculate and output particle size information of atmospheric particulate matter.

At this time, the traditional dynamic light scattering technology has the following shortcomings: (1) Time-consuming, the sample solution needs to be left standing for a long time in the early stage to avoid the influence of directional motion on the measurement results. (2) It is difficult to realize real-time monitoring and measurement.

SUMMARY OF THE INVENTION

Based on this, the purpose of the present invention is to provide an on-line measurement system and method for particle size distribution of atmospheric particles, which can overcome the deficiencies of the existing dynamic light scattering technology, has a simple structure, and does not require a long standing treatment of the sample solution. Real-time online measurement of atmospheric particulate matter.

An online measurement system for particle size distribution of atmospheric particles, comprising a sample collection unit, a peristaltic pump, a measurement unit and a signal processing unit; the measurement unit includes a sample cell, a laser and a detector; the sample collection unit collects atmospheric samples and It is converted into a sample solution, and the peristaltic pump injects the sample solution into the sample cell at least two different speeds respectively; the laser emits laser light to the sample cell containing the sample solution, and the detector detects the peristalsis. The scattered light generated when the pump injects the sample solution at different speeds is converted into scattered photoelectric signals, and the signal processing unit receives the different scattered photoelectric signals and outputs the atmospheric particles according to the injection speed of the different sample solution. Particle size information.

The on-line measurement system for the particle size distribution of atmospheric particles of the present invention can accurately obtain the particle size even under the condition of a flow rate, which makes up for the need for a long standing treatment of the sample particles in the traditional dynamic light scattering technology before measurement. The defect greatly saves the experiment time. This method provides a good technical support for the measurement of atmospheric particles dissolved in fluids. At the same time, the implementation is simple, the later signal processing process is easy to understand, and real-time measurement is realized, which provides a strong basis for monitoring and adjusting the behavior of the particle system in time, and effectively improves the online measurement technology of atmospheric particles based on dynamic light scattering technology.

Further, the peristaltic pump injects the sample solution into the sample cell at at least four different speeds respectively, the signal processing unit receives at least four groups of different scattered photoelectric signals, and injects the sample into the at least four groups about the peristaltic pump. The velocity of the solution and the data of the particle size of the atmospheric particles are fitted with a polynomial not lower than the third order to obtain a particle size-velocity relationship, so as to output the particle size information of the atmospheric particles.

Further, the sample collection unit further includes a vacuum pump and a wet collection device; the vacuum pump collects gas containing atmospheric particles and injects it into the wet collection device at a constant speed to convert it into a sample solution.

Further, the measuring unit further includes a convex lens; the convex lens condenses the scattered light generated by the laser light passing through the sample cell.

Further, the measurement unit further comprises an optical fiber; the scattered light is condensed by the convex lens and then transmitted to the detector through the optical fiber.

Further, the atmospheric particle measurement unit further includes a light trap; the transmitted light generated by the laser passing through the sample cell is absorbed by the light trap.

Further, the measuring unit further includes a collimating lens; the laser light emitted by the laser is collimated by the collimating lens and then incident into the sample cell.

The present invention also provides an on-line measurement method for particle size distribution of atmospheric particles, comprising the following steps:

S2: inject the sample solution into the sample cell at at least two different speeds, and inject laser light into the sample cell at the same time, detect the scattered light generated when the sample solution is injected at different speeds, and convert it into a scattered photoelectric signal ;

S3: Receive different scattered photoelectric signals, and combine different sample solution injection speeds to fit and output particle size information of atmospheric particles.

Further, in the step S2, the sample solution is injected into the sample cell at at least four different speeds and the laser light is injected into the sample cell, and the scattered light generated when the sample solution is injected at different speeds is detected, And it is converted into a scattered photoelectric signal; in the step S3, the particle size-velocity is obtained by performing polynomial fitting of at least four sets of data on the speed of the injected sample solution and the particle size of the atmospheric particles that is not lower than the third order Relational expression to output particle size information of atmospheric particles.

Further, in the step S2, the transmitted light generated by the laser passing through the sample cell is absorbed.

For better understanding and implementation, the present invention is described in detail below with reference to the accompanying drawings.

Description of drawings

Figure 1 is a structural diagram of an online measurement system for the particle size distribution of atmospheric particles;

Figure 2 is a schematic structural diagram of the measurement unit.

Detailed ways

The present invention adopts dynamic light scattering technology and combines the idea of polynomial fitting to measure the particle size of atmospheric particles. Specifically, the present application deduces the particle size information of the sample particles through the scattered light signal generated by the laser passing through the sample cell containing the sample solution, and obtains the particle size information of the sample particles obtained under different injection speeds of the sample solution to establish a fitting polynomial, so as to obtain the particle size information of the sample particles in the static state of the sample solution. The specific implementation device is as follows.

Referring to FIG. 1 , an online measurement system for particle size distribution of atmospheric particulates includes a sample acquisition unit 10 , a peristaltic pump 20 , a measurement unit 30 and a signal processing unit 40 which are sequentially arranged in a logical order of use. Specifically, the sample collection unit 10 further includes a vacuum pump 11 and a wet capture device 12 .

The vacuum pump 11 provides power for the entire sample collection unit, and injects gas containing particulate matter into the wet capture device 12; the wet capture device 12 is used to capture the particulate matter in the gas and convert it It is a sample solution containing particulate matter; the peristaltic pump 20 is used to draw the sample solution and send it into the measurement unit 3 at a certain speed, and this speed can be adjusted; the measurement unit 30 is provided with an input port and An output port, and receives a sample solution containing particles with a certain velocity through the input port, and uses dynamic light scattering technology to characterize the particle size of atmospheric particles as a light intensity signal of scattered light, and outputs this signal through the output port to the signal. processing unit 40 . The signal processing unit 40 is electrically connected to the measurement unit 30, and is analyzed and processed by relevant software, hardware and algorithms to finally obtain particle size distribution information of atmospheric particles.

Further, referring to FIG. 2 , the measurement unit 30 includes a sample cell 31 , a laser 32 , a collimating lens 33 , a light trap 34 , a convex lens 35 , an optical fiber 36 and a detector 37 .

The sample cell 31 is provided with a first port 311, the first port 311 is correspondingly connected to the input port provided in the measurement unit 30, and the sample cell 31 receives the sample solution from the peristaltic pump 20 through the port 311; the laser 32 is connected to the The collimating lens 33 is arranged on one side of the vertical arm of the sample cell 31, and the laser beam emitted by the laser 32 is incident on the vertical arm of the sample cell 31 after passing through the collimating lens 33, generating transmitted light and scattered light at the same time. The optical path of the light is unchanged, and the scattered light and the incident light are at an angle of 90°; the light trap 34 is arranged on the optical path generated by the laser 32, so that the sample cell 31 is located between the light trap 34 and the laser 32, for absorbing laser light and passing through the sample cell The transmitted light generated by 31 avoids the reflection of scattered light into the sample cell and the optical fiber to interfere with the measurement results; along the optical path of the scattered light, a convex lens 35, an optical fiber 36 and a detector 37 are arranged in sequence, and the detector 37 is provided with There is a second port 371 , and the second port 371 is correspondingly connected with the output port provided in the measurement unit 30 .

In the measurement unit 30 , the laser beam emitted by the laser 32 is incident on the vertical arm of the sample cell 31 after passing through the collimating lens 33 , and the laser beam emitted by the laser 32 is incident on the vertical arm of the sample cell 31 after passing through the collimating lens 33 . At the same time, the transmitted light and the scattered light are generated. The optical path of the transmitted light remains unchanged. The scattered light and the incident light form an angle of 90°. The transmitted light is absorbed by the light trap 34, and the scattered light is collected by the convex lens 35, and then incident on the optical fiber 36 and transmitted. to detector 37. The detector 37 processes the received scattered light intensity signal and transmits it to the signal processing unit 40 , and analyzes and processes through relevant software, hardware and algorithms, and finally obtains the particle size distribution information of atmospheric particles.

The basic principles of dynamic light scattering technology are as follows:

The scattered light field formula of the detection point P in the scattered light field of atmospheric particles is as follows.

where E ₀ is the electric field at the observation point, N is the total number of particles, ω ₀ is the angular frequency of the incident light, and φ _jd and φ _jc are the phases of the jth particle produced by Brownian motion and directional motion, respectively. I(t) is the light intensity function of the scattered light intensity; G ² (τ) is the autocorrelation function of the scattered light intensity.

where τ and Γ are the correlation time and decay linewidth, respectively, and φ _kd and φ _kc are the phases of the kth particle resulting from Brownian motion and directional motion, respectively. f is the experimental coefficient related to the environment, v is the speed at which the sample particle solution is injected into the sample cell, k and θ ₁ are the physical quantities of the scattering angle function, which represent the rate of change of the scattering angle and the initial scattering angle, respectively.

Finally, the autocorrelation function g ₂ (τ) of the normalized scattered light intensity is obtained by simplification:

Among them, n is the refractive index of the sample solution, l ₁ is the length of the particle scatterer to be measured, λ is the laser wavelength, d is the detection distance, and D is the diffusion coefficient. According to the Stokes–Einstein function relationship, the particle size d information of the sample particles can be obtained. .

Γ=Dq ²

where q is the scattering vector, _kB is the Boltzmann constant, T is the solution temperature, and η is the viscosity coefficient.

When the speed of atmospheric particles injected into the sample cell is different, when the light intensity autocorrelation function is deduced from the dynamic light scattering theory, the attenuation line width is also different, and then there is a certain correlation between the attenuation line width and the particle size value obtained by inversion. , so the extraction of particle size can be achieved.

Example 1

In this embodiment, the second-order polynomial fitting is used to measure the particle size of atmospheric particles. That is to set three different sample solution injection speeds, obtain the particle size information corresponding to each set of speeds, and then fit the second-order fitting function between the injection speed and the measured particle size according to the three sets of speed-particle size information, and find Obtain the particle size information of atmospheric particles when the sample solution is left standing.

In this embodiment, the sample cell 31 is a U-shaped cuvette with good light transmission.

In this embodiment, the laser 32 is a semiconductor laser with high stability of 632 nm and 30 mW.

In this embodiment, the collimating lens 33 selects an aspheric collimating lens that matches the divergence angle of the laser 32 .

In the present embodiment, the light trap 34 has the function that the light absorption efficiency is greater than 0.99.

In this embodiment, the optical fiber 36 is a single-mode optical fiber with good transmission characteristics and low back reflection.

In this embodiment, the detector 37 is a photomultiplier tube with high sensitivity.

The implementation steps of the measurement method of the present embodiment are as follows:

(1) Use the sample collection unit 10 to collect the atmospheric particulate matter solution, inject the sample particle solution into the sample cell 31 at the speed of V ₁ =2.0 mm/s through the peristaltic pump 20 , and form a circulating flow.

(2) The laser 32 of the measuring unit 30 is turned on, the detector 37 collects the light intensity signal, and the corresponding particle size information D ₁ is obtained through the signal processing unit 40 .

(3) Measurement Under the same atmospheric particulate matter sampling environment, the peristaltic pump 20 sequentially performs the above step (2) at different speeds (speeds are V ₂ =4.0mm/s, V ₃ =6.0mm/s) to obtain different The particle size information of V ₂ and V ₃ are D ₂ and D ₃ , respectively.

(4) Determine the quadratic polynomial fitting function. Let the particle size-velocity relationship be D=K ₀ +K ₁ V+K ₂ V ² , where D is the particle size, V is the injection speed of the sample particle solution, and K ₀ , K ₁ , and K ₂ are the fitting coefficients . According to the four sets of data measured in the preceding steps, the following matrix equations can be obtained.

After substituting the velocity value (unit: mm/s), the following equation is obtained.

Invert the velocity matrix and left-multiply the inverse matrix on both sides at the same time to obtain the following equation.

Since the final need is to obtain the particle size information of the atmospheric particles when the velocity is 0, it can be obtained according to the particle size-velocity relationship, K ₀ is the particle size of the atmospheric particles when the velocity is 0. From the above matrix equation we can get:

K ₀ =3D ₁ -3D ₂ +D ₃

That is, the particle size information of the atmospheric particles measured when the sample solution is left standing can be obtained through the above expression.

In the actual experimental process, a standard sample solution with a particle size of 401 nm was used, and the above steps were performed in sequence. When the injection speed is 2.0mm/s, the obtained inversion particle size D ₁ =376.9nm; when the injection speed is 4.0mm/s, the obtained inversion particle size D ₂ =339.9nm; when the injection speed is 6.0mm /s, the obtained inversion particle size D ₃ =287.2 nm.

Substitute the three sets of inversion particle size data into the above expression, and obtain K ₀ =398.2, that is, the particle size measured when the sample solution is left standing is 398.2 nm, with an error of 2.8 nm.

Example 2

In this embodiment, a third-order polynomial fitting is used to measure the particle size of atmospheric particles. That is, set four different sample solution injection speeds, obtain the particle size information corresponding to each set of speeds, and then fit the third-order fitting function between the injection speed and the measured particle size according to the four sets of speed-particle size information. Obtain the particle size information of atmospheric particles when the sample solution is left standing.

(1) Use the sample collection unit 10 to collect the atmospheric particulate matter solution, inject the sample particle solution into the sample cell 31 at the speed of V ₁ =1.0 mm/s through the peristaltic pump 20 , and form a circulating flow.

(3) Measurement Under the same atmospheric particulate matter sampling environment, the peristaltic pump 20 is performed in sequence at different speeds (speeds are V ₂ =3.0mm/s, V ₃ =5.0mm/s, V ₄ =7.0mm/s) In the above step (2), different particle size information is obtained, and the particle size values corresponding to V ₂ , V ₃ , and V ₄ are D ₂ , D ₃ , and D ₄ , respectively.

(4) Determine the cubic polynomial fitting function. Let the particle size-velocity relationship be D=K ₀ +K ₁ V+K ₂ V ² +K ₃ V ³ , where D is the particle size, V is the injection speed of the sample particle solution, K ₀ , K ₁ , K ₂ and _K3 are fitting coefficients. According to the four sets of data measured in the preceding steps, the following matrix equations can be obtained.

K ₀ =2.1875D ₁ -2.1875D ₂ +1.3125D ₃ -0.3125D ₄

In the actual experimental process, a standard sample solution with a particle size of 401 nm was used, and the above steps were performed in sequence. When the injection speed is 1.0mm/s, the obtained inversion particle size D ₁ =400.1nm; when the injection speed is 3.0mm/s, the obtained inversion particle size D ₂ =367.9nm; when the injection speed is 5.0mm /s, the obtained inversion particle size D ₃ =258.1nm; when the injection speed is 7.0mm/s, the obtained inversion particle size D ₄ =30.4nm.

Substitute the three sets of inversion particle size data into the above expression, and obtain K ₀ =399.7, that is, the particle size measured when the sample solution is left standing is 399.7 nm, with an error of 1.3 nm.

Compared with the prior art, the present application does not need to wait for the sample solution injected into the sample cell to decelerate until it is still, but directly obtains the particle size information calculated from the sample solution in the moving state to deduce the particle size information of the sample solution in the static state. , which can save time waiting for the sample solution to stand still, enabling efficient and real-time online measurement.

It can be seen from the comparison of the two embodiments that when the order of the fitting function is higher, the error of the obtained measurement result is smaller and the accuracy is higher. The experimenter can choose the appropriate one according to the actual accuracy requirements order to measure.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any person skilled in the art may use the above-described technical content to change or modify the equivalents of equivalent changes. Example. However, any simple modifications made to the above examples according to the technical essence of the present invention are equivalent to changes and modifications without departing from the technical solution content of the present invention, and still belong to the protection scope of the technical solution of the present invention.

Claims

An on-line measurement system for particle size distribution of atmospheric particles, characterized in that: it includes a sample collection unit, a peristaltic pump, a measurement unit and a signal processing unit; the measurement unit includes a sample cell, a laser and a detector; the sample collection unit collects The atmospheric sample is converted into a sample solution, and the peristaltic pump injects the sample solution into the sample cell at at least two different speeds respectively; the laser emits laser light to the sample cell containing the sample solution, and the detector Detect the scattered light generated when the peristaltic pump injects the sample solution at different speeds, and convert them into scattered photoelectric signals, and the signal processing unit receives the different scattered photoelectric signals and combines the injection speeds of the different sample solutions to fit Output particle size information of atmospheric particles.
The online measurement system for particle size distribution of atmospheric particles according to claim 1, wherein the peristaltic pump injects the sample solution into the sample cell at at least four different speeds respectively, and the signal processing unit receives at least four different speeds. Four groups of different scattered photoelectric signals, by performing polynomial fitting of at least four groups of data about the speed of the peristaltic pump injected into the sample solution and the particle size of atmospheric particles, the particle size-velocity relationship is obtained, and output Size information of atmospheric particles.
The online measurement system for particle size distribution of atmospheric particles according to claim 2, characterized in that: the sample collection unit further comprises a vacuum pump and a wet collection device; the vacuum pump collects gas containing atmospheric particles and injects it at a constant speed The wet acquisition device to convert it into a sample solution.
The online measurement system for particle size distribution of atmospheric particles according to claim 3, characterized in that: the measurement unit further comprises a convex lens; the convex lens condenses the scattered light generated by the laser passing through the sample cell.
The online measurement system for particle size distribution of atmospheric particles according to claim 4, characterized in that: the measurement unit further comprises an optical fiber; the scattered light is condensed by the convex lens and transmitted to the detector through the optical fiber.
The online measurement system for particle size distribution of atmospheric particulate matter according to claim 3, characterized in that: the atmospheric particulate matter measuring unit further comprises a light trap; the transmitted light generated by the laser passing through the sample cell is absorbed by the light trap.
The online measurement system for particle size distribution of atmospheric particles according to any one of claims 1-6, characterized in that: the measurement unit further comprises a collimating lens; the laser light emitted by the laser is collimated by the collimating lens directly into the sample cell.
An on-line measurement method for particle size distribution of atmospheric particulates, characterized in that it comprises the following steps:

S1: Collect atmospheric samples containing atmospheric particles and convert them into sample solutions;

S2: inject the sample solution into the sample cell at at least two different speeds, and inject laser light into the sample cell at the same time, detect the scattered light generated when the sample solution is injected at different speeds, and convert it into a scattered photoelectric signal ;

S3: Receive different scattered photoelectric signals, and combine different sample solution injection speeds to fit and output particle size information of atmospheric particles.
The on-line measurement method for particle size distribution of atmospheric particulates according to claim 8, characterized in that: in the step S2, the sample solution is injected into the sample cell at at least four different speeds and injected into the sample cell at the same time. The laser detects the scattered light generated when the sample solution is injected at different speeds, and converts it into scattered photoelectric signals; Perform a polynomial fitting of not lower than the third order on the data of , to obtain a particle size-velocity relationship to output particle size information of atmospheric particles.
The online method for measuring the particle size distribution of atmospheric particulates according to claim 8, wherein in the step S2, the transmitted light generated by the laser passing through the sample cell is absorbed.