CN108956517A - A kind of real-time online continuously monitors the device and its application method of sulfate concentration - Google Patents

A kind of real-time online continuously monitors the device and its application method of sulfate concentration Download PDF

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Publication number
CN108956517A
CN108956517A CN201811058109.5A CN201811058109A CN108956517A CN 108956517 A CN108956517 A CN 108956517A CN 201811058109 A CN201811058109 A CN 201811058109A CN 108956517 A CN108956517 A CN 108956517A
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China
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concentration
sulfate
real
cuvette
time online
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张治国
艾新玉
李磊朋
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light

Abstract

A kind of real-time online continuously monitors the device and its application method of sulfate concentration, and the present invention relates to devices and its application method that a kind of real-time online continuously monitors sulfate concentration.The present invention is in order to solve the problems, such as to be difficult to realize precise measurement.Apparatus of the present invention include deuterium lamp, the first lens, the first sample introduction pipeline, the second sample introduction pipeline, cuvette, pump, drain line, waste liquid pool, the second lens, optical fiber, spectrometer and computer.The method of the present invention is using deuterium lamp as ultraviolet source, and Maya2000 spectrometer, by measuring the OP value of various concentration sulfate radical solution, provides the calibration curve between OP value and concentration in the cuvette of sulfate radical solution injection circulation as detector.By in testing liquid injection device system, its OP value is measured.Further according to calibration curve, corresponding sulfate concentration is obtained, the present invention provides a kind of methods that real-time online continuously monitors sulfate concentration.The present invention is applied to concentration monitor field.

Description

A kind of real-time online continuously monitors the device and its application method of sulfate concentration
Technical field
The present invention relates to devices and its application method that a kind of real-time online continuously monitors sulfate concentration.
Background technique
In recent years, flue gas largely discharges, serious to destroy ecological ring due to a large amount of burnings of coal in industrial production Border.SO in flue gas3Although discharge amount seldom, since more and more coal-burning power plants of China are mounted with selective catalytic reduction Denitrification apparatus, SO2It is oxidized to SO to a certain extent3, lead to SO3Increase, Acid Rain Pollution aggravates, and corrosion range is wider.Cause This, country has put into effect a series of schemes, has formulated about SO3The discharge standard of pollutant has important meaning for environmental protection Justice.Therewith, each coal-burning power plant is dedicated to SO3Content is monitored, and is proposed the method for flue gas condensing, by flue gas liquid The measurement of sulfate concentration reflects SO indirectly in sample3Content.
Currently, the chromatography of ions, titration, gravimetric method, atomic spectroscopy, ultraviolet-visible spectrophotometry, fluorescence method and Electrochemical process etc. is used equally for the detection of sulfate radical.Wherein, ultraviolet-visible spectrophotometry is more common, have conveniently, it is simple, Good selective, application are very extensive.But since the irradiation of long-time light source can cause solution temperature in cuvette to rise, Absorption spectrum and the measurement of OP value is caused deviation occur, it is difficult to realize precise measurement.
Summary of the invention
The present invention causes to inhale to solve solution temperature in cuvette can be caused to rise since long-time light source irradiates at present There is deviation in the measurement for receiving spectrum and OP value, it is difficult to which the problem of realizing precise measurement provides a kind of real-time online and continuously monitor The device and its application method of sulfate concentration.
A kind of device that real-time online continuously monitors sulfate concentration of the present invention includes deuterium lamp, the first lens, the first sample introduction Pipeline, the second sample introduction pipeline, cuvette, pump, drain line, waste liquid pool, the second lens, optical fiber, spectrometer and computer, wherein the For one lens between deuterium lamp and cuvette, the inlet of the first sample introduction pipeline and the second sample introduction pipeline is inserted respectively into cuvette It is interior, and the first sample introduction pipeline and the second sample introduction pipeline are arranged in parallel, and cuvette bottom end is provided with liquid flowing outlet, drain line Inlet is connected to liquid flowing outlet, and liquid outlet is connected to waste liquid pool, and pump is equipped in drain line, and the second lens are located at colorimetric Between ware and optical fiber, optical fiber is connect with spectrometer, and spectrometer is connect by data line with computer.
The physical principle of apparatus of the present invention is the light that deuterium lamp issues ultraviolet band, is entered through being received after cuvette by optical fiber Spectrometer.Solution concentration changes in cuvette, and spectrometer signal changes, and realizes detection.Concrete operating principle is sulphur Acid group solution enters Flow-injection System by sample introduction pipeline, and under the irradiation of deuterium lamp-ultraviolet source, sulfate radical exists in solution There is very strong UV absorption in 160~220nm wavelength band, by the absorption spectrum and OP that measure various concentration sulfate radical solution Value, determines the calibration curve of OP and sulfate concentration.According to calibration curve, by the OP value for surveying testing liquid sulfate radical Corresponding sulfate concentration is provided, reflects SO in flue gas indirectly3Content.
The characteristics of apparatus of the present invention, is:
The present invention makes sulfate radical solution be constantly in circulation status using pump, eliminates under light source irradiates for a long time and causes temperature The influence risen, and it is able to verify that whether the OP value of sulfate radical solution under the conditions of long-time ultraviolet light can change.
The present invention using pump carry out solution extraction operation, control its extract rate it is identical with sample rate, make in cuvette Solution level remains unchanged.
Signal conversion may be implemented by using Maya2000 spectrometer in the present invention.
The present invention using deuterium lamp and Maya2000 spectrometer as light source and detection device, it is low in cost, dress is effectively reduced It is set to this, there is practicability.
A kind of method that real-time online continuously monitors sulfate concentration of the present invention sequentially includes the following steps:
One, using ultrapure water as sample back end, ultrapure water is delivered to cuvette by the first sample introduction pipeline, spectrometer will The received optical signal of optical fiber is converted to digital signal, and computer connects spectrometer and carries out data record, obtains the ultraviolet transmission of back end Spectrum;
Two, pumping takes the ultrapure water in cuvette through drain line into waste liquid pool;
Three, sulfuric acid standard solution is injected into cuvette by the second sample introduction pipeline, handles to obtain sulfate radical using computer Ultra-violet absorption spectrum and OP value;
Four, pumping takes the sulfuric acid standard solution in cuvette through drain line into waste liquid pool;
Five, the operation that step three and four is repeated using the sulfuric acid standard solution of various concentration, handles to obtain not using computer With the ultra-violet absorption spectrum and OP value of concentration sulfate radical;
Six, the calibration curve between the OP value of various concentration sulfate radical and concentration is made using Origin software;
Seven, the sulfate radical solution of concentration to be measured is injected into cuvette by the second sample introduction pipeline, handles to obtain using computer The ultra-violet absorption spectrum and OP value of sulfate radical, the then calibration between the OP value and concentration of the sulfate radical according to obtained in step 6 Curve, correspondence obtain the concentration of sulfate radical in sulfate radical solution to be measured;
Eight, after monitoring, ultrapure water device is utilized.
The method of the present invention is using deuterium lamp as light source, and Maya2000 spectrometer infuses sulfate radical solution as detector Enter in the cuvette of circulation, by measuring the OP value of various concentration sulfate radical solution, the calibration provided between OP value and concentration is bent Line.By in testing liquid injection device system, its OP value is measured.Further according to the calibration curve between sulfate radical OP and concentration, obtain To corresponding sulfate concentration, a kind of simple and easy method for realizing sulfate concentration measurement is provided.
The characteristics of the method for the present invention, is:
The OP value for surveying various concentration sulfate radical solution in the present invention by ultraviolet absorption spectroscopy, so that it is determined that OP value and sulphur Calibration curve between acid group concentration.
The invention has the advantages that:
The present invention provides one kind based on circulation one spectrometer of cuvette, the one flow injection ultraviolet absorption spectroscopy of deuterium lamp one The method for measuring sulfate concentration in testing liquid, this method are continuous by using the real-time online that pump realizes sulfate concentration Monitoring eliminates under light source irradiates for a long time and causes the influence of temperature rise, and is able to verify that sulfuric acid under the conditions of long-time ultraviolet light Whether the OP value of root solution can change.It is detected simultaneously using deuterium lamp and Maya2000 spectrometer, instrument is simple, operation side Just, it is easy to accomplish the measurement of sulfate concentration under various extreme environmental conditions.
The present invention has detected the various concentration sulfate radical solution in flow injection state using ultraviolet absorption spectroscopy OP value, give the calibration curve of OP value and sulfate concentration, it can be achieved that in testing liquid sulfate concentration accurate detection, It is reversed to reflect SO in flue gas3Content.The real-time online that the present invention realizes sulfate concentration continuously monitors, to the minimum inspection of sulfate radical Can be reached by surveying limit by 0.029 μM.
Detailed description of the invention:
Fig. 1 is the real-time online continuous monitoring method apparatus structure schematic diagram of sulfate concentration of the present invention:
Fig. 2 is the uv absorption spectra of the various concentration sulfate radical obtained using method of the invention;
Fig. 3 is the standard curve using method OP value and sulfate concentration obtained of the invention;
Fig. 4 is the OP value variation for continuously monitoring various concentration sulfate radical on-line using method of the invention.
Specific embodiment
Specific embodiment 1: the device that a kind of real-time online of present embodiment continuously monitors sulfate concentration includes deuterium lamp 1, the first lens 2, the first sample introduction pipeline 3, the second sample introduction pipeline 4, cuvette 5, pump 6, drain line 7, waste liquid pool 8, second are saturating Mirror 9, optical fiber 10, spectrometer 11 and computer 12, wherein the first lens 2 are between deuterium lamp 1 and cuvette 5, the first sample introduction pipeline 3 It is inserted respectively into cuvette 5 with the inlet of the second sample introduction pipeline 4, and the first sample introduction pipeline 3 and the second sample introduction pipeline 4 are flat Row setting, 5 bottom end of cuvette is provided with liquid flowing outlet, and the inlet of drain line 7 be connected to liquid flowing outlet, liquid outlet with give up Liquid pool 8 is connected to, and pump 6 is equipped in drain line 7, the second lens 9 are between cuvette 5 and optical fiber 10, optical fiber 10 and spectrum Instrument 11 connects, and spectrometer 11 is connect by data line with computer 12.
The physical principle of present embodiment device is the light that deuterium lamp issues ultraviolet band, is received through after cuvette by optical fiber Into spectrometer.Solution concentration changes in cuvette, and spectrometer signal changes, and realizes detection.Concrete operating principle Flow-injection System is entered by sample introduction pipeline for sulfate radical solution, under the irradiation of deuterium lamp-ultraviolet source, sulfuric acid in solution Root has very strong UV absorption in 160~220nm wavelength band, by the absorption spectrum for measuring various concentration sulfate radical solution With OP value, the calibration curve of OP and sulfate concentration is determined.According to calibration curve, by the OP value for surveying testing liquid sulfate radical Corresponding sulfate concentration can be provided, reflects SO in flue gas indirectly3Content.
The characteristics of present embodiment device, is:
Present embodiment makes sulfate radical solution be constantly in circulation status using pump, eliminates under light source irradiates for a long time and draws The influence of temperature rise is played, and is able to verify that whether the OP value of sulfate radical solution under the conditions of long-time ultraviolet light can change.
Present embodiment using pump carry out solution extraction operation, control its extract rate it is identical with sample rate, make colorimetric Solution level remains unchanged in ware.
Signal conversion may be implemented by using Maya2000 spectrometer in present embodiment.
Present embodiment is using deuterium lamp and Maya2000 spectrometer as light source and detection device, low in cost, effective drop Low installation cost has practicability.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: cuvette 5 is equipped with top cover, top It covers and is provided with two holes, the first sample introduction pipeline 3 and the second sample introduction pipeline 4 are fixedly connected by two holes with cuvette top cover respectively.Its It is same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: cuvette 5 is rule Lattice are the quartz colorimetric utensil of 10mm.It is other identical as one of specific embodiment one or two.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: deuterium lamp 1 is located at the One lens, 2 focal point.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: optical fiber 10 is located at Second lens, 9 focal point.It is other identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: spectrometer 11 is Maya2000 spectrometer.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: 1 wavelength of deuterium lamp is 160~280nm.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: a kind of real-time online of present embodiment continuously monitors the method for sulfate concentration by following step It is rapid to carry out:
One, using ultrapure water as sample back end, ultrapure water is delivered to cuvette 5, spectrometer by the first sample introduction pipeline 3 The received optical signal of optical fiber 10 is converted to digital signal by 11, and computer 12 connects spectrometer 11 and carries out data record, obtains back end Ultraviolet transmission spectrum;
Two, the ultrapure water in 6 extraction cuvette 5 of pump is through drain line 7 into waste liquid pool 8;
Three, sulfuric acid standard solution is injected into cuvette 5 by the second sample introduction pipeline 4, is handled using computer 12 and obtains sulfuric acid The ultra-violet absorption spectrum and OP value of root;
Four, the sulfuric acid standard solution in 6 extraction cuvette 5 of pump is through drain line 7 into waste liquid pool 8;
Five, the operation that step three and four is repeated using the sulfuric acid standard solution of various concentration is handled using computer 12 and is obtained Less than the ultra-violet absorption spectrum and OP of concentration sulfate radical;
Six, the calibration curve between the OP value of various concentration sulfate radical and concentration is made using Origin software;
Seven, the sulfate radical solution of concentration to be measured is injected into cuvette 5 by the second sample introduction pipeline 4, is handled using computer 12 The ultra-violet absorption spectrum and OP value of sulfate radical are obtained, then between the OP value and concentration of the sulfate radical according to obtained in step 6 Calibration curve, correspondence obtain the concentration of sulfate radical in sulfate radical solution to be measured;
Eight, after monitoring, ultrapure water device is utilized.
The method of present embodiment is using deuterium lamp as light source, and Maya2000 spectrometer is as detector, by sulfate radical In the cuvette of solution injection circulation, by measuring the OP value of various concentration sulfate radical solution, provide between OP value and concentration Calibration curve.By in testing liquid injection device system, its OP value is measured.It is bent further according to the calibration between sulfate radical OP and concentration Line obtains corresponding sulfate concentration, provides a kind of simple and easy method for realizing sulfate concentration measurement.
The characteristics of this method, is:
The OP value of various concentration sulfate radical solution is obtained by ultraviolet absorption spectroscopy in present embodiment, so that it is determined that OP Calibration curve between value and sulfate concentration.
Present embodiment the utility model has the advantages that
Present embodiments provide for one kind based on circulation one spectrometer of cuvette, the one flow injection UV absorption light of deuterium lamp one The method that spectrometry measures sulfate concentration in testing liquid, this method realize the real-time online of sulfate concentration by using pump Continuous monitoring eliminates under light source irradiates for a long time and causes the influence of temperature rise, and is able to verify that under the conditions of long-time ultraviolet light Whether the OP value of sulfate radical solution can change.It is detected simultaneously using deuterium lamp and Maya2000 spectrometer, instrument is simple, operation It is convenient, it is easy to accomplish the measurement of sulfate concentration under various extreme environmental conditions.
It is molten that present embodiment using ultraviolet absorption spectroscopy has detected the various concentration sulfate radical in flow injection state The OP value of liquid, give the calibration curve of OP value and sulfate concentration, it can be achieved that in testing liquid sulfate concentration accurate inspection It surveys, reflects SO in flue gas indirectly3Content.The real-time online that present embodiment realizes sulfate concentration continuously monitors, to sulphur Acid group minimum detection limit can reach 0.029 μM.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: in step 1 ultrapure water into Sample volume is 2mL.It is other identical as specific embodiment eight.
Specific embodiment 10: present embodiment is unlike specific embodiment eight or nine: sulfuric acid standard solution Sampling volume is 2mL.It is other identical as specific embodiment eight or nine.
The method that a kind of real-time online of embodiment 1, the present embodiment continuously monitors sulfate concentration sequentially includes the following steps:
One, using ultrapure water as sample back end, ultrapure water is delivered to cuvette 5, spectrometer by the first sample introduction pipeline 3 The received optical signal of optical fiber 10 is converted to digital signal by 11, and computer 12 connects spectrometer 11 and carries out data record, obtains back end Ultraviolet transmission spectrum;
Two, the ultrapure water in 6 extraction cuvette 5 of pump is through drain line 7 into waste liquid pool 8;
Three, sulfuric acid standard solution is injected into cuvette 5 by the second sample introduction pipeline 4, utilizes Ocean in computer 12 Optics SpectraSuite software obtains the ultra-violet absorption spectrum and OP value of sulfate radical;
Four, the sulfuric acid standard solution in 6 extraction cuvette 5 of pump is through drain line 7 into waste liquid pool 8;
Five, the operation that step three and four is repeated using the sulfuric acid standard solution of various concentration, utilizes Ocean in computer 12 Optics SpectraSuite software obtains the ultra-violet absorption spectrum and OP of various concentration sulfate radical;
Six, the calibration curve between the OP value of various concentration sulfate radical and concentration is made using Origin software;
Seven, the sulfate radical solution of concentration to be measured is injected into cuvette 5 by the second sample introduction pipeline 4, using in computer 12 Ocean Optics SpectraSuite software obtains the ultra-violet absorption spectrum and OP value of sulfate radical, then according in step 6 Calibration curve between the OP value and concentration of sulfate radical, correspondence obtain the concentration of sulfate radical in sulfate radical solution to be measured;
Eight, after monitoring, ultrapure water device is utilized.
As shown in Figure 1, the device that the present embodiment real-time online continuously monitors sulfate concentration includes deuterium lamp 1, the first lens 2, the first sample introduction pipeline 3, the second sample introduction pipeline 4, cuvette 5, pump 6, drain line 7, waste liquid pool 8, the second lens 9, optical fiber 10, Spectrometer 11 and computer 12, wherein the first lens 2 are between deuterium lamp 1 and cuvette 5, the first sample introduction pipeline 3 and the second sample introduction The inlet of pipeline 4 is inserted respectively into cuvette 5, and the first sample introduction pipeline 3 and the second sample introduction pipeline 4 are arranged in parallel, than 5 bottom end of color ware is provided with liquid flowing outlet, and the inlet of drain line 7 is connected to liquid flowing outlet, and liquid outlet and waste liquid pool 8 connect It is logical, pump 6 is equipped in drain line 7, between cuvette 5 and optical fiber 10, optical fiber 10 and spectrometer 11 connect the second lens 9 It connects, spectrometer 11 is connect by data line with computer 12.
Fig. 2 is the uv absorption spectra of the various concentration sulfate radical obtained using method of the invention;Wherein 1 is 0.001M, 2 be 0.002M, 3 be 0.003M, 4 be 0.004M, 5 be 0.005M, 6 be 0.006M.Fig. 3 is using side of the invention The standard curve of method OP value and sulfate concentration obtained, the concentration of sulfate radical solution to be measured can be measured according to Fig. 3;Fig. 4 For the OP value variation for continuously monitoring various concentration sulfate radical on-line using method of the invention.The present embodiment is to the minimum inspection of sulfate radical Can be reached by surveying limit by 0.029 μM.

Claims (10)

1. the device that a kind of real-time online continuously monitors sulfate concentration, it is characterised in that it is dense that real-time online continuously monitors sulfate radical The device of degree includes deuterium lamp (1), the first lens (2), the first sample introduction pipeline (3), the second sample introduction pipeline (4), cuvette (5), pump (6), drain line (7), waste liquid pool (8), the second lens (9), optical fiber (10), spectrometer (11) and computer (12), wherein first Lens (2) are located between deuterium lamp (1) and cuvette (5), the inlet point of the first sample introduction pipeline (3) and the second sample introduction pipeline (4) It is not inserted into cuvette (5), and the first sample introduction pipeline (3) and the second sample introduction pipeline (4) are arranged in parallel, cuvette (5) bottom End is provided with liquid flowing outlet, and the inlet of drain line (7) is connected to liquid flowing outlet, and liquid outlet is connected to waste liquid pool (8), Drain line (7) is equipped with pump (6), and the second lens (9) are located between cuvette (5) and optical fiber (10), optical fiber (10) and spectrum Instrument (11) connection, spectrometer (11) are connect by data line with computer (12).
2. the device that a kind of real-time online according to claim 1 continuously monitors sulfate concentration, it is characterised in that colorimetric Ware (5) is equipped with top cover, is provided with two holes on top cover, the first sample introduction pipeline (3) and the second sample introduction pipeline (4) respectively by two holes and than Color ware top cover is fixedly connected.
3. the device that a kind of real-time online according to claim 1 or 2 continuously monitors sulfate concentration, it is characterised in that ratio Color ware (5) is the quartz colorimetric utensil that specification is 10mm.
4. the device that a kind of real-time online according to claim 1 continuously monitors sulfate concentration, it is characterised in that deuterium lamp (1) it is located at the first lens (2) focal point.
5. the device that a kind of real-time online according to claim 1 continuously monitors sulfate concentration, it is characterised in that optical fiber (10) it is located at the second lens (9) focal point.
6. the device that a kind of real-time online according to claim 1 continuously monitors sulfate concentration, it is characterised in that spectrum Instrument (11) is Maya2000 spectrometer.
7. the device that a kind of real-time online according to claim 1 continuously monitors sulfate concentration, it is characterised in that deuterium lamp (1) wavelength is 160~280nm.
8. carrying out real-time online using the device that real-time online described in claim 1 continuously monitors sulfate concentration continuously to monitor The method of sulfate concentration, it is characterised in that this method sequentially includes the following steps:
One, using ultrapure water as sample back end, ultrapure water is delivered to cuvette (5), spectrometer by the first sample introduction pipeline (3) (11) optical fiber (10) received optical signal being converted into digital signal, computer (12) connects spectrometer (11) and carries out data record, Obtain the Ultraviolet transmission spectrum of back end;
Two, pump (6) extracts the ultrapure water in cuvette (5) through in drain line (7) to waste liquid pool (8);
Three, by sulfuric acid standard solution by the second sample introduction pipeline (4) injection cuvette (5), sulphur is obtained using computer (12) processing The ultra-violet absorption spectrum and OP value of acid group;
Four, pump (6) extracts the sulfuric acid standard solution in cuvette (5) through in drain line (7) to waste liquid pool (8);
Five, the operation that step three and four is repeated using the sulfuric acid standard solution of various concentration is obtained not using computer (12) processing With the ultra-violet absorption spectrum and OP value of concentration sulfate radical;
Six, the calibration curve between the OP value of various concentration sulfate radical and concentration is made using Origin software;
Seven, by the sulfate radical solution of concentration to be measured by the second sample introduction pipeline (4) injection cuvette (5), at computer (12) Reason obtains the ultra-violet absorption spectrum and OP value of sulfate radical, then between the OP value and concentration of the sulfate radical according to obtained in step 6 Calibration curve, correspondence obtain the concentration of sulfate radical in sulfate radical solution to be measured;
Eight, after monitoring, ultrapure water device is utilized.
9. the method that a kind of real-time online according to claim 8 continuously monitors sulfate concentration, it is characterised in that step The sampling volume of ultrapure water is 2mL in one.
10. the method that a kind of real-time online according to claim 8 continuously monitors sulfate concentration, it is characterised in that sulfuric acid The sampling volume of standard solution is 2mL.
CN201811058109.5A 2018-09-11 2018-09-11 A kind of real-time online continuously monitors the device and its application method of sulfate concentration Pending CN108956517A (en)

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