CN212255082U - Flame atomizer and trace sodium on-line monitoring system - Google Patents
Flame atomizer and trace sodium on-line monitoring system Download PDFInfo
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- CN212255082U CN212255082U CN202021006208.1U CN202021006208U CN212255082U CN 212255082 U CN212255082 U CN 212255082U CN 202021006208 U CN202021006208 U CN 202021006208U CN 212255082 U CN212255082 U CN 212255082U
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Abstract
The utility model discloses a flame atomizer and trace sodium on-line monitoring system, belonging to the technical field of on-line analysis instruments, wherein the flame atomizer comprises an atomizer chamber, a first chamber, a second chamber and a third chamber which are sequentially communicated; the atomizer chamber is provided with a sample injection capillary tube, an oilless compressed air inlet and an atomizer chamber outlet, and the atomizer chamber outlet is communicated with the atomizer chamber and the first cavity; the first chamber is provided with a gas inlet and an impact ball, and the impact ball is arranged right opposite to the outlet of the atomizer chamber; the second chamber is provided with a high-temperature gas inlet and is filled with the phase-change heat storage balls; a burner is arranged above the third chamber, a purified air inlet is formed in the burner, and an annular central porous combustion head of the burner is communicated with the third chamber. The technical scheme can effectively solve the technical problems of low atomization rate, low flame temperature, unstable flame combustion and the like of the conventional flame atomizer.
Description
Technical Field
The invention relates to the technical field of online analytical instruments, in particular to a flame atomizer and trace sodium online monitoring system.
Background
The flame atomizer is an important component of a spectrometer, is a device for converting ions in a test solution into atomic vapor by utilizing flame, and has great influence on the sensitivity and repeatability of a spectral (atomic absorption, atomic fluorescence spectrum and flame atomic emission spectrum) method. A conventional Flame atomizer (flameatomizer) consists of three parts, an atomizer, a premixing chamber and a burner. In the flame atomization process, a liquid sample is atomized and brought into the flame for atomization by mixing combustion-supporting gas (air or oxygen) and fuel gas (gas fuel), and the sample liquid is introduced into the flame and atomized to undergo a series of complex physical and chemical processes, wherein the process comprises the stages of desolventizing, evaporating, dissociating and the like of fog particles, and most ions are dissociated into gaseous atoms in the dissociation process.
At present, a traditional flame atomizer is used in a second-order differential flame emission spectrometer, a burner adopts normal-temperature (ambient temperature) air to support combustion, and the flame temperature is low and unstable, so that the flame combustion is unstable, and the atomization efficiency is low. Meanwhile, the sample introduction of the traditional atomizer usually adopts a pneumatic concentric atomizer, the atomizer utilizes compressed air with certain pressure as a combustion-supporting device to enter the atomizer, a water sample is sprayed out from the periphery of a sample introduction capillary at high speed, and the introduced combustion-supporting gas is scattered into droplets (aerosol). The more water samples are atomized, the finer the fog drops are, the easier the fog drops are to dry, melt and vaporize, the more free atoms are generated, and the higher the sensitivity of the spectrometer is. However, the highest atomization efficiency of the conventional atomizer can only reach about 10%, and the sensitivity of the second-order differential flame emission spectrometer is low because less than 10% of the test solution is atomized. In order to improve the sensitivity of a second-order differential flame emission spectrometer, the invention has the following patent: 2011.1.0279428.0 adopts oxygen-enriched acetylene flame, utility model: ZL 201620667866.2 used a hydrogen-oxygen flame to increase the flame temperature. However, the combustion speed of the oxygen-enriched-acetylene flame and the hydrogen-oxygen flame is too high during the use of the measures, so that the backfire explosion accident is easily caused, and the use safety of users and instruments is threatened.
Disclosure of Invention
The invention mainly aims to provide a flame atomizer and a trace sodium online monitoring system, and aims to solve the technical problems of low atomization efficiency, low flame temperature, unstable flame combustion and the like of the conventional flame atomizer.
In order to achieve the aim, the invention provides a flame atomizer, which comprises an atomizer chamber, a first chamber, a second chamber and a third chamber which are sequentially communicated; the atomizer chamber is provided with a sample injection capillary tube, an oil-free compressed air inlet and an atomizer chamber outlet, and the atomizer chamber outlet is communicated with the atomizer chamber and the first cavity; the first chamber is provided with a gas inlet and an impact ball, and the impact ball is arranged right opposite to the atomizer chamber outlet; the second chamber is provided with a high-temperature air inlet and is filled with phase-change heat storage balls; the top of third chamber is provided with the combustor, the combustor is provided with the air-purifying entry, just the porous burning head intercommunication in annular center of combustor the third chamber.
Optionally, separation flanges are respectively arranged between the first chamber and the second chamber and between the second chamber and the third chamber, and the separation flanges are provided with through holes to respectively communicate the first chamber with the second chamber and communicate the second chamber with the third chamber.
Optionally, the flame atomizer further comprises an electrolytic high-purity water hydrogen generator, and an outlet of the electrolytic high-purity water hydrogen generator is communicated with the fuel gas inlet.
Optionally, the flame atomizer still includes oil-free air compressor, precision air heater, membrane dryer and filtration clarifier, oil-free air compressor's export sets up a pressure regulating valve, pressure regulating valve's exit linkage to the entry of membrane dryer, the export of membrane dryer is through first isolation valve intercommunication oil-free compressed air entry, the export of membrane dryer is connected to through the second isolation valve precision air heater's entry, precision air heater's export intercommunication the high temperature gas entry, the export of membrane dryer is through filtration clarifier intercommunication the air purification entry.
Optionally, the first chamber is further provided with a waste liquid discharge port, and one side of the third chamber is further provided with an explosion-proof membrane.
Optionally, a vacuum annular cavity is arranged in the side wall of the second chamber to realize heat preservation treatment of the second chamber.
Optionally, the phase-change heat storage ball comprises a stainless steel ball shell with a cavity, and a charging sealing port is arranged on the stainless steel ball shell so as to fill the phase-change heat storage material in the cavity of the stainless steel ball shell.
Optionally, the phase change temperature of the phase change heat storage material is 400 ℃.
In addition, in order to achieve the above object, the present invention further provides an online trace sodium monitoring system, which includes a sample introduction-calibration component, a second-order differential flame emission spectrometer and the above flame atomizer, wherein the sample introduction-calibration component is configured to sequentially, continuously and stably transport high purity water for calibration, a standard water sample and a water sample to be measured to the atomizer chamber of the flame atomizer through the sample introduction capillary under the control of the second-order differential flame emission spectrometer; the flame atomizer is used for sequentially atomizing and flame-atomizing the high-purity calibration water, the standard water sample and the water sample to be measured which are conveyed by the sample introduction-calibration assembly under the control of the second-order differential flame emission spectrometer to form flame with 589.0nm sodium spectrum radiation; the second-order differential flame emission spectrometer is used for controlling the operation of the sample introduction-calibration assembly and the flame atomizer in real time, and analyzing and processing data of flame formed by the flame atomizer in real time to obtain a corresponding test result.
Optionally, the sample introduction-calibration assembly comprises a high-position high-purity water cup for calibration, a high-position standard water sample cup for calibration, a calibration switching electromagnetic valve, a water sample inlet pipe to be measured, a water sample inlet regulating electromagnetic valve, a sample introduction three-way valve, a water sample inlet pipe and a constant liquid level overflow water sample cup, the water sample inlet pipe to be measured is connected to the first inlet of the sample three-way valve through the water sample inlet regulating electromagnetic valve, the outlet of the high-position high-purity water cup for calibration and the outlet of the high-position standard water sample cup for calibration are respectively connected to the second inlet of the sample injection three-way valve through the calibration switching electromagnetic valve, one end of the water sample inlet pipe is connected to the outlet of the sample injection three-way valve, the other end of the water sample inlet pipe is inserted into the constant liquid level overflow water sample cup, the outer end of the sample injection capillary is inserted into the constant liquid level overflow water sample cup, and the outlet of the water sample inlet pipe is lower than the inlet of the sample injection capillary.
Optionally, the sample feeding-calibration assembly further comprises a fixing groove and an overflow water collecting cup, and the constant liquid level overflow water sample cup is installed in the overflow water collecting cup through the fixing groove.
Optionally, the second order differential flame emission spectrometer comprises: the photoelectric sensor assembly is used for rapidly scanning the characteristic spectral line of sodium and automatically deducting background interference of flame to generate a second-order differential modulation sodium spectrum so as to be received and excited by a photomultiplier to generate second-order differential frequency modulation current, and the second-order differential frequency modulation current is demodulated and amplified by a phase-locked amplifier and then is output to the data acquisition assembly; the data acquisition assembly is used for acquiring an analog signal of the second-order differential frequency modulation current, converting the analog signal into a digital signal and outputting the digital signal to the embedded industrial personal computer assembly for real-time monitoring and control; and the embedded industrial personal computer component is used for controlling the operation of the sample introduction-calibration component, the flame atomizer, the photoelectric sensor component and the data acquisition component in real time, and carrying out statistical analysis and processing on data acquired by the data acquisition component in real time to obtain a test result.
The flame atomizer comprises an atomizer chamber, a first chamber, a second chamber and a third chamber which are sequentially communicated. The atomizer chamber is provided with a sample injection capillary tube, an oilless compressed air inlet and an atomizer chamber outlet, when the atomizer chamber is used, the outer end of the sample injection capillary tube can be inserted into the constant liquid level overflow water sample cup, at the moment, the oilless compressed air which is accessed through the oilless compressed air inlet forms a negative pressure field in the atomizer chamber, so that a water sample to be measured (or high-level high-purity water for calibration or high-level standard water sample for calibration) in the constant liquid level overflow water sample cup can be sucked into the atomizer chamber through the sample injection capillary tube, and the water sample is sprayed out through the atomizer chamber outlet after the atomization and primary mixing processes of the water sample are completed in the atomizer. The first cavity is provided with gas inlet and impact ball, and the impact ball is just setting up atomizer chamber export, can hit the garrulous to atomizer chamber export spun droplet through the impact ball, makes the fog grain of aerosol more slight, more even. Meanwhile, the fuel gas accessed through the fuel gas inlet can enter the second chamber after being mixed with aerosol sprayed from the outlet of the atomizer chamber in the first chamber. The second cavity is provided with a high-temperature gas inlet, the phase-change heat storage balls are filled in the second cavity, high-temperature gas enters the phase-change heat storage balls through the high-temperature gas inlet and heats the phase-change heat storage balls, and therefore mist particles sprayed out of the atomizer chamber and impacted and crushed by the impact balls are fully contacted with the high-temperature phase-change heat storage balls, the mist particles are heated and completely vaporized, and the atomization efficiency can reach 100%. The burner is arranged above the third chamber, the burner is provided with a purified air inlet, an annular central porous combustion head of the burner is communicated with the third chamber, and purified air (combustion-supporting gas) with stable pressure can be accessed through the purified air inlet, so that the completely atomized high-temperature mixed gas with stable temperature coming out of the second chamber enters the third chamber, and can be ignited above the annular central porous combustion head of the burner to form flame, and the sodium characteristic spectrum with stable spectral line intensity of 589.0nm is radiated. Therefore, the technical scheme can effectively solve the technical problems of low atomization rate, low flame temperature, unstable flame combustion and the like of the conventional flame atomizer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art 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 for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an overall structural diagram of a phase-change heat-storage constant-temperature flame atomizer according to an embodiment of the present invention.
Fig. 2 is a schematic structural view of a phase-change heat storage ball of the flame atomizer shown in fig. 1.
Fig. 3 is a block diagram of a trace sodium online monitoring system according to a second embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a sample injection-calibration assembly of the trace sodium on-line monitoring system shown in fig. 3.
FIG. 5 is a structural block diagram of an embedded industrial personal computer of a second-order differential flame emission spectrometer of the trace sodium online monitoring system shown in FIG. 3.
FIG. 6 is a block diagram of a specific calibration process of the calibration module of the embedded industrial personal computer shown in FIG. 5
FIG. 7 is a Roman gold plot of atomic emission spectroscopy.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
As shown in fig. 1, the first embodiment of the present invention provides a flame atomizer ii, which includes an atomizer chamber 110, a first chamber 120, a second chamber 130, and a third chamber 140, which are sequentially connected. The atomizer chamber 110 is provided with a sample injection capillary tube 111, an oil-free compressed air inlet 112 and an atomizer chamber outlet 113, and the atomizer chamber outlet 113 communicates the atomizer chamber 110 with the first chamber 120. The first chamber 120 is provided with a gas inlet 121 and a striking ball 122, the striking ball 122 being disposed directly opposite the atomizer chamber outlet 113. The second chamber 130 is provided with a high temperature gas inlet 131, and the second chamber 130 is filled with the phase change thermal balls 132. A burner 141 is arranged above the third chamber 140, the burner 141 is provided with a purified air inlet 142, and an annular central porous combustion head of the burner 141 is communicated with the third chamber 140.
In the embodiment, as shown in fig. 1, the separation flanges 10 are disposed between the first chamber 120 and the second chamber 130, and between the second chamber 130 and the third chamber 140, and the separation flanges 10 have through holes 11 to respectively communicate the first chamber 120 with the second chamber 130, and the second chamber 130 with the third chamber 140. Thus, the partition flange 10 having the through hole 11 can partially communicate with the first chamber 120, the second chamber 130, and the third chamber 140 while partitioning them.
As shown in fig. 2, phase-change heat storage ball 132 includes a stainless steel ball housing 1321 with a cavity, and a charging sealing port 1322 is disposed on stainless steel ball housing 1321 to fill phase-change heat storage material 1323 in the cavity of stainless steel ball housing 1321. Specifically, the stainless steel ball shell 1321 is a stainless steel hollow ball with the diameter of 8mm-16mm, the feeding sealing port 1322 is sealed by filling a stainless steel plug coated with high-temperature-resistant glue into an outer hole, the volume of the phase change heat storage material 1323 is 2/3-3/4 of the volume of the stainless steel ball shell, the phase change heat storage material 1323 is a solid-solid composite phase change material, and the phase change temperature of the solid-solid composite phase change heat storage material is designed to be 400 ℃. The second chamber 130 is a "phase-change thermal storage atomizing bed" filled with phase-change thermal storage balls 132, and the mist particles of the aerosol sprayed from the atomizer chamber 110 and impacted and pulverized by the impact balls 122 are fully contacted and atomized with the high-temperature phase-change thermal storage balls 132, and the atomization efficiency can reach 100%.
As shown in fig. 1, the flame atomizer ii in the present embodiment further includes an electrolytic high-purity water hydrogen generator 150, an oil-free air compressor 160, a precision air heater 170, a membrane dryer 180, and an air filtration purifier 190. Wherein, the outlet of the electrolysis high-purity water hydrogen generator 150 is communicated with the fuel gas inlet 121, and high-purity hydrogen is connected to the fuel gas inlet 121 as fuel gas, so that the combustion stability of the burner can be further ensured. The outlet of the oil-free air compressor 160 is provided with a pressure regulating valve 12, the outlet of the pressure regulating valve 12 is connected to the inlet of the membrane dryer 180, the outlet of the membrane dryer 180 is communicated with the oil-free compressed air inlet 112 through a first isolation valve 13, the outlet of the membrane dryer 180 is connected to the inlet of the precision air heater 170 through a second isolation valve 14, the outlet of the precision air heater 170 is communicated with a high-temperature gas inlet 131, and the outlet of the membrane dryer 180 is communicated with a purified air inlet 142 through an air filtering purifier 190. That is, the "purified air" introduced into the purified air inlet 142 in this embodiment is the clean air obtained by further removing solid and liquid particles from the air by the dried air output from the outlet of the membrane dryer 180 through the air filtering purifier 190 (specifically, a 0.1 μ precision filter). The 'purified air' enters the annular channel of the annular central porous combustion head from the purified air inlet 142 at the bottom of the combustor 141, and because the pressure of the 'purified air' is higher than that of the combustion mixed gas in the third chamber 140, an annular protective cover with micro-positive pressure is formed around a flame torch for radiating sodium element emission spectrum formed above the combustor 141, and the annular protective cover has the function of automatically diffusing to the periphery of the flame, so that various trace interference components (salt mist and dust particles) in the surrounding space environment can be effectively prevented from entering the center of the atomized flame, and the purposes of performing trace analysis and obtaining a stable measurement result under the common measurement environment condition can be realized.
In addition, as shown in fig. 1, the first chamber 120 is further provided with a waste liquid discharge port 123 to discharge waste liquid. An explosion proof membrane 143 is further provided at one side of the third chamber 140 to ensure safety of the third chamber 140 when the burner 142 is operated. A vacuum annular cavity 133 is disposed in the sidewall of the second chamber 130 to perform a thermal insulation process on the second chamber 130.
During operation, the stable pressure oil-free compressed air that oil-free air compressor 160 exported after pressure adjustment of pressure regulating valve 12 gets into atomizer room 110 through oil-free compressed air entry 112, form "negative pressure field" in atomizer room 110 in order to measure the water sample of measureing (or mark with high-order high-purity water, or mark with high-order standard water sample) and inhale through advancing sample capillary 111, and accomplish the atomizing and preliminary mixing process of water sample in atomizer room 110, spout by atomizer room exit 113 again, at this moment, striking ball 122 in first cavity 120 can crash the fog droplet of atomizer room exit 113 spun into pieces, make the fog grain of aerosol more slight, more even. Meanwhile, the high purity hydrogen output from the electrolyzed high purity hydrogen generator 150 enters the first chamber 120 from the fuel gas inlet 121, mixes with the aerosol sprayed from the atomizer chamber 110, and enters the second chamber 130. Since the second chamber 130 is a phase-change thermal storage atomizing bed filled with the phase-change thermal storage balls 132, the mist particles of the aerosol sprayed from the atomizer chamber 110 and impacted and pulverized by the impact balls 122 are sufficiently contacted with the high-temperature phase-change thermal storage balls 130, and the mist particles are heated and completely vaporized, and the atomizing efficiency can reach 100%. Finally, the fully atomized temperature stable high temperature mixed gas from the second chamber 130 enters the third chamber 140 and is ignited above the annular central porous burner head of the burner 141 to form a flame, radiating a sodium characteristic spectrum with line intensity of 589.0 nm.
In addition, when the flame atomizer II is used, the following operations can be performed: (1) starting the oil-free air compressor 160, adjusting the pressure regulating valve 12 to enable the outlet pressure of the oil-free air compressor 160 to be 0.25MP, closing the first isolation valve 13, opening the second isolation valve 14 to heat the compressed air through the precision air heater 170, and controlling the outlet temperature of the precision air heater 170 to be 400 +/-5 ℃; (2) high-temperature air enters the phase-change heat-storage atomizing bed (i.e. the second chamber 130) through the high-temperature gas inlet 131, and the high-temperature air contacts the phase-change heat storage balls 132 and heats the phase-change heat storage balls 132; until the hot air temperature at the outlet of the burner 141 is stabilized at the phase-change temperature of +5 ℃ (3), the second isolation valve 14 is closed, the first isolation valve 13 is opened, the combustion-supporting gas enters the atomizer chamber 110 through the combustion-supporting gas inlet (i.e. the oil-free compressed air inlet 112), so that a negative pressure field is formed in the atomizer chamber 110, the water sample to be measured enters the atomizer chamber 110 through the sample injection capillary 111 and is atomized into fine droplets, enters the phase-change heat accumulation atomization bed (i.e. the second chamber 130) and is atomized by contacting with the constant-temperature phase-change heat accumulation ball 132, and the glowing constant-temperature high-temperature mixed gas is ignited above the outlet of the burner 141 to form a temperature-stable high-temperature flame and radiate the characteristic emission spectrum of Na element.
Compared with the prior art, the embodiment of the invention has the advantages that: (1) the atomization efficiency is as high as 100%, and the atomization efficiency of the traditional flame atomic absorption atomizer is generally less than 10%, so that the sensitivity of the trace sodium analysis of the embodiment of the invention is improved by one order of magnitude compared with a second-order differential flame emission spectrometer adopting the traditional concentric atomizer. (2) The use of the phase-change heat-storage atomizing bed realizes the high-temperature preheating of the combustion-supporting gas, improves the atomization temperature and improves the sensitivity and detection limit of analysis. (3) The use of the phase-change heat-storage atomizing bed realizes the constant temperature and high temperature of the premixed gas, so that the temperature of the atomized flame is stable, and the repeatability of the measurement result is improved. (4) The detection limit of the second-order differential flame emission spectrometry for measuring the trace sodium in the high-purity water reaches an advanced level of less than 0.1 mu g/L. (5) Compared with graphite furnace atomic absorption spectrometers and inductively coupled plasma emission spectrometers (ICP), the method has the obvious advantages of simple equipment, simple operation and low analysis cost.
Example two
As shown in fig. 3, the second embodiment of the present invention provides an online trace sodium monitoring system, which includes a sample introduction-calibration component i, a flame atomizer ii, and a second-order differential flame emission spectrometer iii. The sample introduction-calibration assembly I is mainly used for sequentially and stably conveying high-purity water for calibration, a standard water sample and a water sample to be measured to an atomizer chamber 110 of a flame atomizer II through a sample introduction capillary tube 111 under the control of a second-order differential flame emission spectrometer III. The flame atomizer II is mainly used for sequentially atomizing and flame atomizing the high-purity calibration water, the standard water sample and the water sample to be measured which are conveyed by the sample injection-calibration assembly I under the control of the second-order differential flame emission spectrometer III to form flame with 589.0nm sodium spectrum radiation. The second-order differential flame emission spectrometer III is mainly used for controlling the operation of the sample introduction-calibration assembly I and the flame atomizer II in real time, and analyzing and processing data of flame formed by the flame atomizer II in real time to obtain a corresponding test result.
In this embodiment, as shown in fig. 4, the sample-calibration assembly i includes a high-level high-purity water cup 201 for calibration, a high-level standard water sample cup 202 for calibration, a calibration switching solenoid valve 203, a water sample inlet pipe 204 to be measured, a water sample inlet regulating solenoid valve 205, a three-way sample valve 206, a water sample inlet pipe 207 and a constant level overflow water sample cup 208, the water sample inlet pipe 204 to be measured is connected to a first inlet of the three-way sample valve 206 via the water sample inlet regulating solenoid valve 205, an outlet of the high-level high-purity water cup 201 for calibration and an outlet of the high-level standard water sample cup 202 for calibration are connected to a second inlet of the three-way sample valve 206 via the calibration switching solenoid valve 203, one end of the water sample inlet pipe 207 is connected to an outlet of the three-way sample valve 206, the other end of the water sample inlet pipe 207 is inserted into the, and the outlet of the water sample inlet pipe 207 is lower than the inlet of the sample capillary 111. During operation, the high-level high-purity water cup 201 for calibration is filled with high-level high-purity water for calibration, the high-level standard water sample cup 202 for calibration is filled with a standard water sample (i.e. a 10 μ g/L sodium standard water sample), and the water sample inlet pipe 204 for water sample to be measured is connected to the water sample to be measured. Through the respective switching of the calibration switching electromagnetic valve 203, the water sample inlet adjusting electromagnetic valve 205 and the sample introduction three-way valve 206, the high purity water for calibration, the standard water sample and the water sample to be measured can be continuously and stably conveyed into the atomizer chamber 110 of the flame atomizer II through the water sample inlet pipe 207, the constant liquid level overflow water sample cup 208 and the sample introduction capillary 111 in sequence.
Specifically, as shown in fig. 4, the sample feeding-calibration assembly i further includes a fixing groove 209 and an overflow water collecting cup 210, and the constant-liquid-level overflow water sample cup 208 is installed in the overflow water collecting cup 210 through the fixing groove 209. The calibration switching solenoid valve 203 is a two-position three-way solenoid valve, and the three channels are respectively connected with the high-position high-purity water cup 201 for calibration, the high-position standard water sample cup 202 for calibration and the sample injection three-way valve 206. The other two paths of the sample three-way valve 206 communicated with the calibration switching electromagnetic valve 203 are respectively communicated with a water sample inlet adjusting electromagnetic valve 205 and a water sample inlet pipe 207. The high-level high-purity water cup 201 for calibration and the high-level standard water sample cup 202 for calibration may be an open Polyethylene (PE) container with a volume of 1000mL and a lower opening, the bottom of the container is a cone-shaped funnel structure, and the height difference between the bottom of the container and the inlet of the sample capillary 111 is a second preset height difference (preferably about 1000 mm). The high-purity water for calibration is high-purity water used for preparing a standard water sample for current calibration. The outlet of the water sample inlet pipe 207 is lower than the inlet of the sample capillary 111 by a first preset height difference (preferably about 10 mm), and the sample capillary 111 is connected to the atomizer chamber 110 of the flame atomizer from the bottom of the constant liquid level overflow water sample cup 208. The constant level overflow water sample cup 208 is preferably a 125mL standard PE narrow mouth sampling bottle placed in a cylindrical holding tank 209 in the center of the open overflow collection cup 210, the cylindrical holding tank 209 being of the size: phi 52 multiplied by 50(H), the flow rate of the water sample flowing through the constant liquid level overflow water sample cup 208 is designed to be 40mL/min-60 mL/min. The overflow port of the constant liquid level overflow water sample cup 208 is the bottle mouth of a 125mL standard PE narrow-mouth sampling bottle, the overflow function of the constant liquid level overflow water sample cup 208 is to keep the height of a liquid column of a water sample at the inlet of the sample injection capillary 111 stable in the measurement process, the stable height of the water sample can stabilize the static pressure at the inlet of the sample injection capillary 111, and the stable lifting amount of the water sample entering the atomizer can be ensured under the condition that the pressure of carrier gas (hydrogen and oxygen mixed gas) is stable by keeping the static pressure at the inlet of the sample injection capillary 111 stable. The stability of flame combustion temperature in the measurement process can be guaranteed due to the stability of the water sample lifting amount, so that the stability and repeatability of the measurement result are guaranteed. Meanwhile, the water sample overflows from the top of the constant liquid level overflow water sample cup 208, so that the real-time performance of the water sample measured in the constant liquid level overflow water sample cup 208 is guaranteed. The design ensures that the outlet of the water sample inlet pipe 207 is lower than the inlet of the sample capillary 111 by a first preset height difference (about 10 mm), and the real-time performance of the water sample entering the sample capillary 111 can be ensured, so that the real-time representativeness of the measured data is ensured.
The second-order differential flame emission spectrometer (III) specifically comprises a photoelectric sensor component, a data acquisition component and an embedded industrial personal computer component. The photoelectric sensor assembly is mainly used for rapidly scanning characteristic spectral lines of sodium and automatically deducting background interference of flame to generate a second-order differential modulation sodium spectrum so as to receive and excite a second-order differential frequency modulation current generated by a photomultiplier, and the second-order differential frequency modulation current is demodulated and amplified by a phase-locked amplifier and then is output to the data acquisition assembly. The data acquisition assembly is mainly used for acquiring analog signals of second-order differential frequency modulation current and converting the analog signals into digital signals to be output to the embedded industrial personal computer assembly for real-time monitoring and control. The embedded industrial personal computer component is mainly used for controlling the operation of the sample introduction-calibration component I, the flame atomizer II, the photoelectric sensor component and the data acquisition component in real time, and performing statistical analysis and processing on data acquired by the data acquisition component in real time to obtain a test result.
The embedded industrial personal computer component specifically comprises an embedded industrial personal computer (host) and a resistance-type touch screen (display), the embedded industrial personal computer can be used for processing and displaying digital signals transmitted by a lower computer, and the host and the slave are communicated by a USB. Therefore, the user can write various functional programs on the upper computer to effectively inquire and analyze the data in the file, and the long-term normal operation and check in the analysis and measurement process are facilitated. As shown in fig. 5, the embedded industrial personal computer includes a system setting module 301, an ignition module 302, a calibration module 303, a measurement module 304, and a data processing module 305.
The system setting module 301: the device is used for setting the characteristic spectral line wavelength of an automatic scanning second-order differential precision grating monochromator to be 589.0 nm; the photoelectric multiplier is also used for setting the ripple coefficient of the high-voltage direct current voltage output by the negative high-voltage module of the photomultiplier to be less than 0.005%, the maximum drift to be less than +/-0.03%/h and the negative high-voltage direct current voltage value. In terms of operation, after a user turns on a host power supply, a monochromator power supply, a silicon nitride ignition power supply and a computer power supply, a USB connecting cable is used for connecting an industrial personal computer and a lower computer (host), and the computer and the monochromator. And starting an icon of trace sodium online monitoring software, and completing the step of system setting in a software man-machine interface dialog box, wherein the parameters of the system setting include but are not limited to system time setting, characteristic spectral line wavelength setting of 589.0nm, photomultiplier negative high voltage setting and user name setting. After the setting is completed, the computer performs system detection, and the detected parameters include but are not limited to: the device comprises an electrolytic high-purity water hydrogen generator output pressure, a flame sensor state signal, a silicon nitride automatic ignition power switch state, an oil-free air compressor output pressure signal, a calibration state signal, a calibration switching solenoid valve state signal, a sample introduction three-way valve state signal, a water sample inlet adjusting solenoid valve state signal and the like.
The ignition module 302: the ignition solenoid valve is used for starting the electrolytic high-purity water hydrogen generator 150, and after the output pressure of the electrolytic high-purity water hydrogen generator 150 is detected to reach the preset ignition threshold value and the automatic ignition power supply is normal, the ignition solenoid valve is started.
The calibration module 303: and the sampling-calibrating assembly I is used for controlling the sampling-calibrating assembly I to sequentially and stably convey the high-purity water for calibration and the standard water sample for calibration to the flame atomizer II after detecting that the state signal of the flame sensor is normal, and sending a data acquisition instruction to the data acquisition assembly to acquire the measurement data of the water sample for calibration acquired by the data acquisition assembly. In particular, the amount of the solvent to be used,
it should be noted that before the calibration module 303 starts the calibration process, the high-level high-purity water cup 201 for calibration and the high-level standard water sample cup 202 for calibration need to be filled with high-purity water and sodium standard water samples (10 μ g/L), respectively. As shown in fig. 6, the specific calibration process of the calibration module 303 includes:
and S110, closing the water sample inlet regulating electromagnetic valve 205.
S120, opening the calibration switching electromagnetic valve 203 and tangentially calibrating the high-position high-purity water cup 201.
S130, opening the sample three-way valve 206 to enable the high-purity water to flow into the constant-liquid-level overflow water sample cup 208.
Specifically, after the sample inlet three-way valve 206 is opened, the high-purity water flows into the constant-liquid-level overflow water sample cup 208 through the sample inlet water pipe 207, the high-purity water from the high-level high-purity water cup 201 for calibration is automatically sucked into the atomizer chamber 110 through the sample inlet capillary 111 to complete the atomization, mixing and droplet separation processes, and then the flame with the radiation of 589.0nm sodium spectrum is formed by ignition above the outlet of the annular central porous combustion head of the combustor 141.
And S140, sending a data acquisition command to the data acquisition assembly, and acquiring a measurement result of the high purity water acquired by the data acquisition assembly.
Specifically, the embedded industrial personal computer sends an acquisition instruction to a single chip microcomputer of the data acquisition assembly, and the single chip microcomputer acquires a direct current analog signal from a low-pass filter of the micro-current phase-locked amplifier, converts the direct current analog signal into a digital signal through an A/D converter and sends the digital signal to the embedded industrial personal computer for storage and further processing.
S150, the calibration switching electromagnetic valve 203 is opened, the high-level standard water sample cup 202 for tangential calibration is opened, and after the preset time is flushed, the measurement result of the standard water sample collected by the data collection assembly is obtained.
Specifically, after the high-purity water sample introduction reading is finished, the calibration switching solenoid valve 203 is used for tangentially calibrating the high-level standard water sample cup 202, a 10 mu g/L sodium standard water sample flows into the constant-liquid-level overflow water sample cup 208, data collection is started after 3 minutes of flushing, and data collection of the 10 mu g/L sodium standard water sample is finished.
And S160, closing the calibration switching electromagnetic valve 203, and opening the water sample inlet adjusting electromagnetic valve 205.
S170, obtaining a calibrated regression line and the sodium background concentration of the high-purity air white water.
Specifically, sodium ions in a water sample are atomized in a high-temperature flame and excite a "characteristic spectral line" of the sodium ions, and under the condition that the concentration of the sodium ions is extremely low (trace), the intensity of the spectral line is in direct proportion to the concentration of the sodium ions in the sample according to the roman equation (as shown in fig. 7).
Wherein, the physical meaning of the Roman formula is: the calibration curve of the atomic emission spectrum must be a straight line passing through the origin (the measured value of the line intensity can be zero if and only if the sodium ion concentration in the water sample is zero), which provides a theoretical basis for the measurement calibration of the atomic emission spectrum without the need to prepare "no sodium water", and in fact, under the prior art conditions, true "no sodium water" does not exist in the laboratory. Whereas "sodium free water" was recognized and used as a prerequisite for atomic absorption and liquid chromatography for the measurement of trace amounts of sodium.
Namely:
y＝fbx (1)
x＝y/fb (2)
in the formula: x is the true concentration of sodium (mug/L) in the water sample;
y is the spectral line intensity value (instrument spectral line intensity meter reading muA)
fbThe slope of the regression line.
Setting:
the No. 0 water sample is high-purity air white water:
setting sodium background concentration x of high-purity air white water0＝C0(μg/L)；
Measuring the spectral line intensity value y of the high-purity air white water0；
Then: y is0＝fbx0 (3)
Setting No. 1 water sample as high purity blank water sample with added sodium content xSStandard solution of (2):
let the sodium concentration of the No. 1 water sample be x1(μ g/L), and the intensity value y of the measured spectral line1；
Then: y is1＝fbx1 (4)
x1＝x0+xS(true sodium concentration of # 1 Water sample) (5)
Substituting formula (5) for formula (4) to obtain:
fb＝y1/(x0+xs) (6)
the formula (6) is substituted into the formula (3) to obtain the sodium background concentration of the high-purity air white water:
x0(C0)＝y0xs/(y1-y0) (7)
the slope is obtained by substituting formula (7) for formula (6):
fb＝(y1-y0)/xs (8)
substituting formula (8) into Lomakin-Scherbe formula (1)
Obtaining a calculation formula of the real sodium concentration in the water sample:
x＝y/fb＝xsy/(y1-y0) (9)
in the embodiment, the sodium background concentration C of the high-purity air white water is automatically given through automatically calculating the calibration result0[μg/L]Regression line graphs (i.e., roman curves) of values and calibration results. From the derivation process described above, it can be seen that: when the 'two-point calibration method' provided by the instrument is used for measuring the trace sodium, the premise of 'no sodium water' is not required, and the real trace sodium content in the water sample can be accurately measured by only using water with the same level as the sodium content of the sample as 'blank' water.
The measurement module 304: and the device is used for controlling the sample introduction-calibration assembly I to continuously and stably convey the water sample to be measured to the flame atomizer II and acquire the measurement data of the water sample to be measured acquired by the data acquisition assembly after detecting that the connection between the sample introduction three-way valve 206 and the calibration switching electromagnetic valve 203 is closed, the water sample inlet adjusting electromagnetic valve 205 is opened and the sample introduction three-way valve 206 is connected to the sample introduction water inlet pipe 207. Specifically, the measurement module 304 closes the water sample inlet adjusting solenoid valve 205 according to a preset frequency, and opens the water sample inlet adjusting solenoid valve 205 after collecting the measurement data. After the calibration module 303 completes the calibration process, the measurement process of the measurement module 304 is automatically performed, that is, the real-time actual sodium concentration of the online water sample is measured according to the instruction of the measurement program. At this time, the connection between the sample three-way valve 206 and the calibration switching solenoid valve 203 is already in a closed state, the sample inlet regulating solenoid valve 205 is already in an open state, and the sample three-way valve 206 is already connected to the sample inlet pipe 207. The water sample from the water sample inlet regulating solenoid valve 205 of the boiler water and steam sampling frame continuously flows through the constant liquid level overflow water sample cup 208. The measuring frequency is preferably 1/10 min, and the industrial personal computer instructs the singlechip to close the water sample inlet regulating electromagnetic valve 205 when the measurement data acquisition is triggered (the real-time water sample measurement is completed by reading every 10 minutes). The water sample inlet regulating solenoid valve 205 is automatically opened immediately after the data acquisition is completed. Thus, the continuous sample introduction and the intermittent static measurement are adopted for programmed analysis operation, and the computer program in the measurement process closes the water sample inlet regulating electromagnetic valve 205 to realize the static measurement of the constant liquid level overflow water sample cup 208, thereby ensuring the real-time representativeness of the measurement result, ensuring the stability of the measurement condition and ensuring the repeatability of the measurement result.
The data processing module 305: and the method is used for carrying out statistical analysis on the measurement data of the calibration water sample and the measurement data of the water sample to be measured in real time to obtain a trace sodium test result. Specifically, each of the output measurement data is an arithmetic average of statistics of 6 parallel measurements at intervals of 1 second, while statistics such as a standard deviation of the measurement result, a relative standard deviation, and "uncertainty" of the measurement result are automatically given. The method can intelligently calibrate and directly display the measurement result on an on-site LCD screen by determining the real-time working curve of the actual sodium concentration of the water sample passing through the origin of coordinates, and the calibrated measurement result is the real sodium content value in the water sample.
The flame atomizer comprises an atomizer chamber, a first chamber, a second chamber and a third chamber which are sequentially communicated. The atomizer chamber is provided with a sample injection capillary tube, an oilless compressed air inlet and an atomizer chamber outlet, when the atomizer chamber is used, the outer end of the sample injection capillary tube can be inserted into the constant liquid level overflow water sample cup, at the moment, the oilless compressed air which is accessed through the oilless compressed air inlet forms a negative pressure field in the atomizer chamber, so that a water sample to be measured (or high-level high-purity water for calibration or high-level standard water sample for calibration) in the constant liquid level overflow water sample cup can be sucked into the atomizer chamber through the sample injection capillary tube, and the water sample is sprayed out through the atomizer chamber outlet after the atomization and primary mixing processes of the water sample are completed in the atomizer. The first cavity is provided with gas inlet and impact ball, and the impact ball is just setting up atomizer chamber export, can hit the garrulous to atomizer chamber export spun droplet through the impact ball, makes the fog grain of aerosol more slight, more even. Meanwhile, the fuel gas accessed through the fuel gas inlet can enter the second chamber after being mixed with aerosol sprayed from the outlet of the atomizer chamber in the first chamber. The second cavity is provided with a high-temperature gas inlet, the phase-change heat storage balls are filled in the second cavity, high-temperature gas enters the phase-change heat storage balls through the high-temperature gas inlet and heats the phase-change heat storage balls, and therefore mist particles sprayed out of the atomizer chamber and impacted and crushed by the impact balls are fully contacted with the high-temperature phase-change heat storage balls, the mist particles are heated and completely vaporized, and the atomization efficiency can reach 100%. The burner is arranged above the third chamber, the burner is provided with a purified air inlet, an annular central porous combustion head of the burner is communicated with the third chamber, and purified air (combustion-supporting gas) with stable pressure can be accessed through the purified air inlet, so that the completely atomized high-temperature mixed gas with stable temperature coming out of the second chamber enters the third chamber, and can be ignited above the annular central porous combustion head of the burner to form flame, and the sodium characteristic spectrum with stable spectral line intensity of 589.0nm is radiated. Therefore, the technical scheme can effectively solve the technical problems of low atomization rate, low flame temperature, unstable flame combustion and the like of the conventional flame atomizer.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (12)
1. The flame atomizer is characterized by comprising an atomizer chamber, a first chamber, a second chamber and a third chamber which are sequentially communicated; the atomizer chamber is provided with a sample injection capillary tube, an oil-free compressed air inlet and an atomizer chamber outlet, and the atomizer chamber outlet is communicated with the atomizer chamber and the first cavity; the first chamber is provided with a gas inlet and an impact ball, and the impact ball is arranged right opposite to the atomizer chamber outlet; the second chamber is provided with a high-temperature gas inlet and is filled with phase-change heat storage balls; the top of third chamber is provided with the combustor, the combustor is provided with the air-purifying entry, just the porous burning head intercommunication in annular center of combustor the third chamber.
2. The flame atomizer according to claim 1, wherein a separation flange is provided between the first chamber and the second chamber, and between the second chamber and the third chamber, and the separation flange is provided with a through hole to communicate the first chamber with the second chamber, and the second chamber with the third chamber, respectively.
3. The flame atomizer according to claim 1, further comprising an electrolytic high purity water hydrogen generator, an outlet of said electrolytic high purity water hydrogen generator being in communication with said fuel gas inlet.
4. The flame atomizer according to claim 1, further comprising an oil-free air compressor, a precision air heater, a membrane dryer, and an air filtration purifier, wherein a pressure regulating valve is disposed at an outlet of the oil-free air compressor, an outlet of the pressure regulating valve is connected to an inlet of the membrane dryer, an outlet of the membrane dryer is communicated with the oil-free compressed air inlet via a first isolation valve, an outlet of the membrane dryer is connected to an inlet of the precision air heater via a second isolation valve, an outlet of the precision air heater is communicated with the high-temperature gas inlet, and an outlet of the membrane dryer is communicated with the purified air inlet via the air filtration purifier.
5. The flame atomizer according to claim 1, wherein said first chamber is further provided with a waste liquid discharge port, and one side of said third chamber is further provided with an explosion-proof membrane.
6. The flame atomizer according to claim 1, wherein a vacuum annular cavity is provided in the sidewall of said second chamber to effect a heat-insulating treatment of said second chamber.
7. A flame atomizer according to any one of claims 1-6, characterized in that said phase change heat storage ball comprises a stainless steel ball shell with a cavity, and a charging seal is arranged on said stainless steel ball shell to fill the cavity of said stainless steel ball shell with phase change heat storage material.
8. The flame atomizer according to claim 7, characterized in that the phase change temperature of said phase change heat storage material is 400 ℃.
9. An online trace sodium monitoring system, which comprises a sample introduction-calibration component, a second order differential flame emission spectrometer and a flame atomizer according to any one of claims 1 to 8,
the sample introduction-calibration assembly is used for sequentially and continuously and stably conveying high-purity water for calibration, a standard water sample and a water sample to be measured to the atomizer chamber of the flame atomizer through the sample introduction capillary under the control of the second-order differential flame emission spectrometer;
the flame atomizer is used for sequentially atomizing and flame-atomizing the high-purity calibration water, the standard water sample and the water sample to be measured which are conveyed by the sample introduction-calibration assembly under the control of the second-order differential flame emission spectrometer to form flame with 589.0nm sodium spectrum radiation;
the second-order differential flame emission spectrometer is used for controlling the operation of the sample introduction-calibration assembly and the flame atomizer in real time, and analyzing and processing data of flame formed by the flame atomizer in real time to obtain a corresponding test result.
10. The online trace sodium monitoring system according to claim 9, wherein the sample-calibration assembly comprises a calibration high-purity water cup, a calibration high-purity standard water sample cup, a calibration switching solenoid valve, a to-be-measured water sample inlet tube, a water sample inlet regulating solenoid valve, a sample three-way valve, a water sample inlet tube and a constant level overflow water sample cup, the to-be-measured water sample inlet tube is connected to a first inlet of the sample three-way valve through the water sample inlet regulating solenoid valve, an outlet of the calibration high-purity water cup and an outlet of the calibration high-purity standard water sample cup are respectively connected to a second inlet of the sample three-way valve through the calibration switching solenoid valve, one end of the water sample inlet tube is connected to an outlet of the sample three-way valve, the other end of the water sample inlet tube is inserted into the constant level overflow water sample cup, and an outer end of the capillary tube is inserted into the constant level overflow, and the outlet of the water sample inlet pipe is lower than the inlet of the sample injection capillary.
11. The online trace sodium monitoring system according to claim 10, wherein the sample injection-calibration assembly further comprises a fixing groove and an overflow water collecting cup, and the constant liquid level overflow water sample cup is mounted in the overflow water collecting cup through the fixing groove.
12. The online trace sodium monitoring system according to claim 9, wherein the second order differential flame emission spectrometer comprises:
the photoelectric sensor assembly is used for rapidly scanning the characteristic spectral line of sodium and automatically deducting background interference of flame to generate a second-order differential modulation sodium spectrum so as to be received and excited by a photomultiplier to generate second-order differential frequency modulation current, and the second-order differential frequency modulation current is demodulated and amplified by a phase-locked amplifier and then is output to the data acquisition assembly;
the data acquisition assembly is used for acquiring an analog signal of the second-order differential frequency modulation current, converting the analog signal into a digital signal and outputting the digital signal to the embedded industrial personal computer assembly for real-time monitoring and control;
and the embedded industrial personal computer component is used for controlling the operation of the sample introduction-calibration component, the flame atomizer, the photoelectric sensor component and the data acquisition component in real time, and carrying out statistical analysis and processing on data acquired by the data acquisition component in real time to obtain a test result.
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| CN112881366A (en) * | 2021-03-20 | 2021-06-01 | 河南中烟工业有限责任公司 | Self-discharging moisture-removing dust-removing device for flame photometer |
| CN112881365A (en) * | 2021-03-20 | 2021-06-01 | 河南中烟工业有限责任公司 | A dust removal heating removes damp device for flame photometer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112881366A (en) * | 2021-03-20 | 2021-06-01 | 河南中烟工业有限责任公司 | Self-discharging moisture-removing dust-removing device for flame photometer |
| CN112881365A (en) * | 2021-03-20 | 2021-06-01 | 河南中烟工业有限责任公司 | A dust removal heating removes damp device for flame photometer |
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