CN103983590A - Device and method for detecting long-light-path liquid sulfide - Google Patents
Device and method for detecting long-light-path liquid sulfide Download PDFInfo
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- CN103983590A CN103983590A CN201410238052.2A CN201410238052A CN103983590A CN 103983590 A CN103983590 A CN 103983590A CN 201410238052 A CN201410238052 A CN 201410238052A CN 103983590 A CN103983590 A CN 103983590A
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Abstract
The invention relates to a device for detecting long-light-path liquid sulfide. A rheostat is connected between a power supply and a light source; a light-preventing shell is arranged on an emergent light path of the light source; a reaction vessel is arranged in the light-preventing shell, and a dosing tube is arranged on the top of the light-preventing shell; a breathable film tube is arranged in the reaction vessel along the radial direction; the breathable film tube is connected with an incident optical fiber through a liquid inlet pipe and is connected with an emergent optical fiber through a liquid outlet pipe; the incident optical fiber is connected with the light source; the emergent optical fiber is connected with a photoelectric converter; the photoelectric converter is connected with a data acquisition unit; the data acquisition unit is connected with a computer. The sulfide overflows from a matrix to be detected by using an acid dosing method, an interference phenomenon of foreign ions existing in the complex pretreatment process is avoided, the measurement selectivity is improved, the pretreatment is not required, the measurement process is simplified, and interference of external light is avoided due to reaction under light-resistant conditions, so that the measurement process is not interfered by impurities, and the analysis efficiency and the detection sensitivity are improved.
Description
Technical field
The invention belongs to chemical analysis instrument studying technological domain, particularly a kind of easy, sensitive, pick-up unit and method of measuring rapidly liquid medium sulphide content.
Background technology
Sulfide refers in water and waste water has deliquescent inorganic sulphide (to comprise H
2s, HS
?and S
2 ?) and the general name of acid soluble metal sulfide, be the Equations of The Second Kind pollutant that State Environmental Protection Administration is assert.Sulfide in solution generally mainly contains three kinds of existence form: H
2s, HS
?, S
2 ?, after adding acid, HS wherein
?, S
2 ?be converted into H
2s, when the concentration of hydrogen sulfide dissolving is greater than its solubleness, sulfuretted hydrogen will overflow from solution.
Sulfide is extensively present in the aqueous solution such as oil field, colliery and smeltery.Sulfide in solution is easy to be converted into sulfuretted hydrogen in the situation that pH reduces and overflows from solution, and this gives life and produces and bring the even health of harm humans of inconvenience.S in oilfield sewage
2 ?iron and steel is had to certain corrosivity, and it can form local corrosion or pitting corrosion at steel surface, finally makes iron and steel tube wall damaged, destroys waterflood system, hinders normally and produces.The product of its corrosion is the gluey FeS suspension of water-fast black, and excellent stability can make the rapid blackening of water after processing smelly, and suspension increases; FeS is a kind of oil emulsion stabilizing agent simultaneously, and it will cause oil removing difficulty to increase on ground, injects the underground injection efficiency that will cause and declines, and stops up stratum, and makes in-place oil emulsion plugging oil impregnate duct, reduces the oil displacement efficiency of water; Also may cause in addition well to be stopped up, the number of times of well-flushing and acidifying be increased, thereby increase opex.And for smeltery, the raw material of some smelteries production and application is the mineral such as antimony, zinc, lead, the metal sulfide that coexisted in ore refines antimony, zinc, copper, nickel, cobalt etc. and all can produce hydrogen sulfide gas from sulphur-bearing ore; Sulfuretted hydrogen is soluble in water, and the waste water that smeltery produces, useless quarrel contain sulfide and directly enter water source, and waste water infiltrates water source by the massif destroying, and causes water body sulphide staining.China < < drinking water sanitary standard > > (GB5749-2006) regulation sulfide content must not surpass 0.02mg/L simultaneously.While containing sulfide in water, because sulfuretted hydrogen spills in air, cause organoleptic indicator to worsen, people cannot use.
At present, the assay method of common liquid medium sulphide content has two kinds to be the methylene blue spectrophotometric method method (GB/T16489 ?1996) of the iodimetric titration measured of water quality sulfide (HJ/T60 ?2000) and water quality sulfide mensuration, iodimetric titration will be carried out complicated pre-service before measuring, acidifying makes hydrogen sulfide gas absorb and generate zinc sulphide from Matrix separation and by zinc acetate solution, zinc sulphide again with excessive iodine effect, remaining iodine and starch storage crop, by sodium thiosulfate solution titrated, finally obtain the content of sulfide; And methylene blue laws is measured after also needing that sulfide acidifying is absorbed to pre-service again.
The pre-treatment that inventor finds above-mentioned two kinds of methods in process of the test is more complicated all, mensuration process is comparatively consuming time, and the light path of ultraviolet-visible pectrophotometer is shorter, in the molecule of all participation reactions, what participate in extinction is sub-fraction wherein, and sensitivity is lower.For the mensuration of sulfide, also have in addition to the above methods fluorescence method, responsive sulfur electrode method, polarography, lead acetate reaction rate method etc., but these methods instrument great majority used are all more expensive, and complicated operation, are inconvenient to carry.
Summary of the invention
In order to overcome the existing deficiency of sulfide pick-up unit of the prior art, the invention provides a kind of preprocessing process of having simplified, optical length, highly sensitive, selectivity is high, analysis efficiency is high and the pick-up unit of the light long light path liquid sulfide being easy to carry about with one.
The present invention also provides a kind of method with said apparatus tracer liquid medium sulphide content.
The present invention realizes the technical scheme that above-mentioned purpose adopts:
A kind of pick-up unit of long light path liquid sulfide, it is by wire, to be connected with rheostat between power supply and light source, on the emitting light path of light source, be provided with lucifuge housing, lucifuge housing is processed with respectively light hole and light hole on relative two side, the center line of light hole and light hole is on emergent light axis, in lucifuge housing, be provided with reaction vessels, top is provided with chemical feed pipe, the outlet of chemical feed pipe extends in reaction vessels, in reaction vessels along being radially provided with ventilated membrane pipe, one end of ventilated membrane pipe is connected with incident optical by feed tube, the other end is connected with outgoing optical fiber by discharging tube, incident optical is connected with the exit end of light source through light hole, outgoing optical fiber is connected with the input end of photoelectric commutator through light hole, the output terminal of photoelectric commutator is connected with data acquisition unit by wire, data acquisition unit is connected with computing machine by wire,
The diameter of above-mentioned ventilated membrane pipe and lenth ratio are 1:10～50, and length is 2～10cm.
Above-mentioned feed tube and discharging tube are T shape tubular construction, and a port of feed tube is connected with incident optical, and another relative port is connected with ventilated membrane pipe, and the 3rd feed liquor port extends to lucifuge hull outside; A port of discharging tube is connected with ventilated membrane pipe, and another port on the other side is connected with outgoing optical fiber, and the 3rd fluid port extends to lucifuge hull outside.
Above-mentioned light source is LED lamp, and wavelength is 500～600nm.
The present invention also provides a kind of detection method of long light path liquid sulfide, and it is comprised of following steps:
(1) to adding in reaction vessels ultrapure water as adding the absorption liquid that pH is 9～13, concentration is 0.01～0.05mol/L in blank solution, ventilated membrane pipe, circulating direction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 500～600nm, light path is 2～10cm, logical optical cross-section diameter and light path ratio are 1:10～50, after 10～50s, in blank solution, add nonvolatile organic acids, outlet end at absorption liquid gathers light intensity, according to A
blank=lg (I
0/ I
t0) calculate blank absorbance;
I wherein
0the mean value of 10～50s light intensity before during for acid filling not; I
t0the real-time light intensity recording during second for t after acid filling;
(2) to adding in reaction vessels, in sulfide sample, ventilated membrane pipe, add the absorption liquid that pH is 9～13, concentration is 0.01～0.05mol/L, circulating direction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 500～600nm, light path is 2～10cm, logical optical cross-section diameter and light path ratio are 1:10～50, after 10～50s, in sulfide sample, add nonvolatile organic acids, outlet end at absorption liquid gathers light intensity, according to A
sample=lg (I
1/ I
t1), calculate the absorbance of sulfide sample;
Wherein: I
1the mean value of 10～50s light intensity before during for acid filling not; I
t1the real-time light intensity recording second for t after acid filling;
(3), according to the sulfide sample absorbance of gained in the blank absorbency value of step (1) gained and step (2), calculate according to the following equation the clean absorbance A of sulfide sample
only:
A
only=A
sample-A
blank;
(4) with calibration curve method, calculate the concentration of institute's test sample product medium sulphide content;
Above-mentioned nonvolatile organic acids is sulfuric acid, phosphoric acid or trichloroacetic acid;
Above-mentioned absorption liquid is sodium nitroprusside solution or methyl green solution.
Principle of work of the present invention:
Utilize sulfide to produce hydrogen sulfide gas under the condition of acid adding, sulfuretted hydrogen overflows see through ventilated membrane tube wall separated with protocorm and enters in ventilated membrane pipe and corresponding reagent reacting from solution, and concrete reaction is as follows:
S
2‐+H
3PO
4＝H
2S+HPO
4 2‐；
HS
‐+H
3PO
4＝H
2S+H
2PO
4 ‐；
H
2s+ absorption liquid → change color
This change color is received by photoelectric commutator and converts light signal to electric signal and is sent to data collecting card, is delivered to computing machine and further processes.
Liquid sulfide pick-up unit and the method for a kind of long light path provided by the invention, it by arranging reaction vessels and ventilated membrane pipe radially being arranged along it in the housing of lucifuge, feed tube is installed respectively at the two ends of ventilated membrane pipe, discharging tube, both guarantee reagent input, can make again light path pass through smoothly, its incident end and exit end all adopt optical fiber transmission leaded light, and utilize photoelectric commutator to gather emergent light signal, and send data acquisition unit to after converting electric signal to, further by computing machine, processed, light source enters from ventilated membrane pipe one end, the other end penetrates, absorption liquid in ventilated membrane pipe and hydrogen sulfide gas generation chromogenic reaction, because light path is longer, the molecule that can guarantee all participation chromogenic reactions all can participate in extinction, greatly improved the sensitivity detecting, and the present invention makes sulfide overflow and then be detected from matrix by the method for acid adding, prevented the interference phenomenon of the foreign ion that exists in complicated preprocessing process, improved the selectivity of measuring, and without pre-service, simplified mensuration process, and the interference of ambient light has been avoided in reaction under lucifuge condition, make mensuration process not disturbed by impurity, improved analysis efficiency.The present invention has also simplified determining instrument, and its apparatus structure is light, is easy to carry, and can directly take the scene of analysis to, carries out Real-Time Monitoring.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of embodiment 1.
Fig. 2 be variable concentrations sodium sulfide solution Xi Guang Du ?time curve.
Fig. 3 is the linear diagram of sodium sulphide standard solution.
Fig. 4 be sodium sulfide solution and interfering ion Xi Guang Du ?time curve.
Embodiment
Now in conjunction with the accompanying drawings and embodiments technical scheme of the present invention is further described, but the present invention is not limited only to following enforcement situation.
Known in conjunction with Fig. 1, the liquid sulfide pick-up unit of the long light path of the present embodiment is to be connected and composed by power supply 1, rheostat 2, light source 3, incident optical 4, lucifuge housing 5, feed tube 6, reaction vessels 7, chemical feed pipe 8, ventilated membrane pipe 9, discharging tube 10, outgoing optical fiber 11, photoelectric commutator 12, data acquisition unit 13, computing machine 14, liquid inlet control valve 15 and discharge opeing operation valve 16.
The light source 3 of the present embodiment is to adopt light emitting diode, it is connected on power supply 1 by wire, for the electric current in regulating circuit, make it be no more than the rated current of light emitting diode, between power supply 1 and light source 3, installed a rheostat 2 additional, can according to actual service condition, select the predominant wavelength of light source 3, for this reaction can be excited in its maximum absorption wave strong point, the predominant wavelength of the LED of selection is consistent with the maximum absorption wavelength of reaction.On the emitting light path of light source 3, be provided with lucifuge housing 5, the lucifuge housing 5 of the present embodiment is the body structure of a shading, require its complete lucifuge, on the left side wall of lucifuge housing 5, be processed with light hole, on right side wall, be processed with light hole, top is processed with dosing mouth, inside is installed with bearing and is arranged on the reaction vessels 7 on bearing with threaded fastener, light hole overlaps with the emergent light axis of light source 3 with the center line of light hole, incident optical 4 is installed on light hole, this incident optical 4 is that non-light absorbent is made, the incident end of incident optical 4 polishes with the exit end of light source 3 and is bonded together, the reaction vessels 7 of the present embodiment can be selected common plastic culture dish, on its left side, on right side wall, on the position relative with light source 3, be processed with mounting hole, the ventilated membrane pipe 9 that polytetrafluoroethylmaterial material is made is radially installed between two mounting holes, this ventilated membrane pipe 9 is long is 3.5cm, diameter of section is 0.2cm, the ratio that is diameter of section and length is 1:17.5, it needs resistant material to make, its porosity is larger, permeability is good, but ventilative assurance liquid is impermeable, at the liquid feeding end of ventilated membrane pipe 9 and a port of feed tube 6, be connected, feed tube 6 is three-port structures, its another port is connected with the other end of incident optical 4, by incident optical 4, be connected with light source 3, the 3rd port of feed tube 6 is feed liquor port, this feed liquor port is through the top of lucifuge housing 5, extend to outside lucifuge housing 5, on this feed liquor port, liquid inlet control valve 15 is installed, can in ventilated membrane pipe 9, add reagent by feed liquor port, the outlet end of ventilated membrane pipe 9 is connected with a port of discharging tube 10, this discharging tube 10 is also three-port structure, its another port is connected with outgoing optical fiber 11, the 3rd port is bleed port, this bleed port also extends to lucifuge housing 5 outsides through lucifuge housing 5, discharge opeing operation valve 16 is installed in bleed port, is opened discharge opeing operation valve 16 and the reagent in ventilated membrane pipe 9 can be discharged.The other end of outgoing optical fiber 11 is polished to input end bonding sliding and photoelectric commutator 12, the model that the photoelectric commutator 12 of the present embodiment can adopt the advanced photoelectricity solution of texas,U.S company to manufacture can be the photoelectric sensor of TSL257, its output terminal is connected with data acquisition unit 13 by wire, data acquisition unit 13 is connected with computing machine 14 by wire, the data of collection is sent to computing machine 14 and is further processed.
In order to make acid solution add convenient and quantitatively add, the chemical feed pipe 8 of an injecting type is installed on the dosing mouth of lucifuge housing 5, the endpiece of this chemical feed pipe 8 extends to the inside of reaction vessels 7, can be to the interior interpolation acid solution of reaction vessels 7.
By the method that above-mentioned long light path liquid medium sulphide content pick-up unit detects, by following step, formed:
(1) in reaction vessels 7, add 0.5mL ultrapure water as blank solution, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.11mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.01mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, light path is 3.5cm, logical optical cross-section diameter is 0.2cm, the ratio of logical optical cross-section diameter and light path is 1:17.5, the phosphoric acid that adds 1mL10% (v/v) in the backward blank solution of 30s, light absorbs through sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, photoelectric commutator 12 Real-time Collection light intensity, by formula A
blank=lg (I
0/ I
t0), calculate blank absorbency value,
I wherein
0the mean value of 30s light intensity before during for acid filling not; I
t0for the real-time light intensity recording during 80s after acid filling;
(2) in reaction vessels 7, add 0.5ml sulfide sample, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.11mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.01mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, logical optical cross-section diameter is 0.2cm, light path is 3.5cm, the ratio of logical optical cross-section diameter and light path is 1:17.5, in the backward sulfide sample of 30s, add 1mL10% (v/v) phosphoric acid, sulfide sample is met acid and is produced hydrogen sulfide gas, hydrogen sulfide gas sees through ventilated membrane pipe and sodium nitroprussiate absorption liquid reacts, light absorbs through reacted sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, photoelectric commutator 12 Real-time Collection light intensity, by formula A
sample=lg (I
1/ I
t1), calculate the absorbance of sulfide sample,
Wherein: I
1the mean value of 30s light intensity before during for acid filling not;
I
t1for recording the real-time light intensity value of 80s after acid filling;
(3) according to A
only=A
sample-A
blankcalculate the clean absorbance of sulfide sample:
(4) with calibration curve method, calculate institute's test sample product medium sulphide content concentration.
Embodiment 2
In the liquid sulfide pick-up unit of the long light path of the present embodiment, ventilated membrane pipe 9 adopts polytetrafluoroethylmaterial material to make, it is long is 2cm, diameter of section is 0.2cm, and the ratio of diameter of section and length is 1:10, and other parts and annexation thereof are identical with embodiment 1.
By the method that above-mentioned long light path liquid medium sulphide content pick-up unit detects, by following step, formed:
(1) in reaction vessels 7, add 0.5mL ultrapure water as blank solution, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.0628mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.10mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, light path is 2cm, logical optical cross-section diameter is 0.2cm, the ratio of logical optical cross-section diameter and light path is 1:10, the phosphoric acid that adds 1mL10% (v/v) in the backward blank solution of 30s, light absorbs through sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity and be converted into magnitude of voltage, by formula A
blank=lg (I
0/ I
t0) calculate blank absorbency,
I wherein
0the mean value of 30s light intensity before during for acid filling not; I
t0for the real-time light intensity recording during 85s after acid filling;
(2) in reaction vessels 7, add 0.5ml sulfide sample, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.0628mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.01mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, logical optical cross-section diameter is 0.2cm, light path is 2cm, the ratio of logical optical cross-section diameter and light path is 1:10, in the backward sulfide sample of 30s, add 1mL10% (v/v) phosphoric acid, sulfide sample is met acid and is produced hydrogen sulfide gas, hydrogen sulfide gas sees through ventilated membrane pipe and sodium nitroprussiate absorption liquid reacts, light absorbs through reacted sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity, by formula A
sample=lg (I
1/ I
t1) can be calculated the absorbance of sulfide sample,
Wherein: I
1the mean value of 30s light intensity before during for acid filling not; I
t1for the real-time light intensity recording during 85s after acid filling;
Other step is identical with embodiment 1.
Embodiment 3
In the liquid sulfide pick-up unit of the long light path of the present embodiment, ventilated membrane pipe 9 adopts polytetrafluoroethylmaterial material to make, it is long is 10cm, diameter of section is 0.2cm, and the ratio of diameter of section and length is 1:50, and other parts and annexation thereof are identical with embodiment 1.
By the method that above-mentioned long light path liquid medium sulphide content pick-up unit detects, by following step, formed:
(1) in reaction vessels 7, add 0.5mL ultrapure water as blank solution, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.314mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.01mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, light path is 10cm, logical optical cross-section diameter is 0.2cm, the ratio of logical optical cross-section diameter and light path is 1:50, the phosphoric acid that adds 1mL10% (v/v) in the backward blank solution of 30s, light absorbs through sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity and be converted into magnitude of voltage, by formula A
blank=lg (I
0/ I
t0) calculate blank absorbency,
I wherein
0the mean value of 30s light intensity before during for acid filling not; I
t0for the real-time light intensity recording during 75s after acid filling;
(2) in reaction vessels 7, add 0.5ml sulfide sample, close discharge opeing operation valve 16, opening liquid inlet control valve 15 is 12 to adding 0.314mL pH in ventilated membrane pipe 9, concentration is the sodium nitroprussiate absorption liquid of 0.01mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 535nm, logical optical cross-section diameter is 0.2cm, light path is 10cm, the ratio of logical optical cross-section diameter and light path is 1:50, in the backward sulfide sample of 30s, add 1mL10% (v/v) phosphoric acid, sulfide sample is met acid and is produced hydrogen sulfide gas, hydrogen sulfide gas sees through ventilated membrane pipe and sodium nitroprussiate absorption liquid reacts, light absorbs through reacted sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity and be converted into magnitude of voltage, by formula A
sample=lg (I
1/ I
t1) can be calculated the absorbance of sulfide sample,
Wherein: I
1the mean value of 30s light intensity before during for acid filling not; I
t1for the real-time light intensity recording during 75s after acid filling;
Other step is identical with embodiment 1.
Embodiment 4
In the detection method of the long light path liquid sulfide of above-described embodiment 1～3, step (1) is to add 0.1mL ultrapure water as blank solution in reaction vessels 7, in ventilated membrane pipe 9, adding 0.2mL pH is 13, concentration is the sodium nitroprussiate absorption liquid of 0.02mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 500nm, the phosphoric acid that adds 1.5mL10% (v/v) in the backward blank solution of 10s, light is after sodium nitroprussiate absorption liquid absorbs, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity and be converted into magnitude of voltage, by formula
A
blank=lg (I
0/ I
t0)
I wherein
0the mean value of 10s light intensity before during for acid filling not; I
t0for the real-time light intensity recording during 70s after acid filling;
Calculate blank absorbency;
(2) in reaction vessels 7, add 0.1ml sulfide sample, to adding 0.2mLpH in ventilated membrane pipe 9, be 13, concentration is the sodium nitroprussiate absorption liquid of 0.02mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 500nm, in the backward sulfide sample of 10s, add 1.5mL10% (v/v) phosphoric acid, sulfide sample is met acid and is produced hydrogen sulfide gas, hydrogen sulfide gas sees through ventilated membrane pipe and sodium nitroprussiate absorption liquid reacts, light absorbs through reacted sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity, by formula A
sample=lg (I
1/ I
t1) can be calculated the absorbance of sulfide sample,
Wherein: I
1the mean value of 10s light intensity before during for acid filling not; I
t1for the real-time light intensity recording during 70s after acid filling;
Other step is identical with corresponding embodiment.
Embodiment 5
In the detection method of the long light path liquid sulfide of above-described embodiment 1～3, step (1) is to add 1mL ultrapure water as blank solution in reaction vessels 7, in ventilated membrane pipe 9, adding 0.24mL pH is 9, concentration is the sodium nitroprussiate absorption liquid of 0.05mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 600nm, the phosphoric acid that adds 2mL10% (v/v) in the backward blank solution of 50s, light is after sodium nitroprussiate absorption liquid absorbs, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity, by formula A
blank=lg (I
0/ I
t0), calculate blank absorbency,
I wherein
0the mean value of 50s light intensity before during for acid filling not; I
t0for the real-time light intensity recording during 90s after acid filling;
(2) in reaction vessels 7, add 1ml sulfide sample, in ventilated membrane pipe 9, adding 0.24mL pH is 9, concentration is the sodium nitroprussiate absorption liquid of 0.05mol/L, circulating direction by incident optical 4 coupling conduction from the liquid feeding end of absorption liquid along absorption liquid passes into the green glow that wavelength is 600nm, in the backward sulfide sample of 50s, add 2mL10% (v/v) phosphoric acid, sulfide sample is met acid and is produced hydrogen sulfide gas, hydrogen sulfide gas sees through ventilated membrane pipe and sodium nitroprussiate absorption liquid reacts, light absorbs through reacted sodium nitroprussiate absorption liquid, at its outlet end, by outgoing optical fiber 11, conduct, utilize photoelectric commutator 12 Real-time Collection light intensity and be converted into magnitude of voltage, by formula A
sample=lg (I
1/ I
t1) calculate the absorbance of sulfide sample,
Wherein: I
1the mean value of 50s light intensity before during for acid filling not; I
t1for the real-time light intensity recording during 90s after acid filling;
Other step is identical with corresponding embodiment.
Embodiment 6
In the detection method of the long light path liquid sulfide of above-described embodiment 1～5, step (1) and step (2) sodium nitroprussiate absorption liquid used can be replaced with the methyl green solution of equivalent same concentrations, and other operation is identical with corresponding embodiment.
Embodiment 7
In the detection method of the long light path liquid sulfide of above-described embodiment 1～5, step (1) and step (2) phosphoric acid used can be replaced with sulfuric acid or the trichloroacetic acid of equivalent, and other operation is identical with corresponding embodiment.
In order to prove beneficial effect of the present invention, applicant has carried out a large amount of experimental verifications, existing take Linear Experiment, detection limit experiment and interference experiment and describes as example, specific as follows:
1, Linear Experiment
Experiment reagent: 0.01mol/L, the sodium nitroprusside solution of pH=12; 10% phosphoric acid; Sodium sulphide standard solution: 0.5～100 μ mol/L
Experimentation: select the LED of 535nm, the length of ventilated membrane pipe is 3.5cm, and internal diameter is 2mm, tests at normal temperatures and pressures according to the method for above-described embodiment 1, and experimental result as shown in Figure 2.
As seen from Figure 2, when acid adding not, in ventilated membrane pipe, the absorbance of solution is substantially constant; When 30s, add phosphoric acid, can obviously find out that absorbance increases rapidly, prove that having sulfuretted hydrogen from solution, to overflow with the liquid in ventilated membrane pipe has occurred to react, along with the concentration increase of sulfide, the variation of its signal is also more obvious, proves that the sulfuretted hydrogen discharging is more, while getting 80s each concentration absorbance do A ?c figure, as Fig. 3.
By Fig. 3, can show that it is 0.016～1.6mg/L at 0.5～100 μ mol/L that the method is measured the range of linearity of sulfide, linear relationship is good, and linear equation is: y=0.0037x+0.0081, R
2=0.9983.
2, detection limit experiment
In formula: DL represents detection limit; K is the coefficient definite according to certain confidence level, and IUPAC nomenclature advises that its value gets the sensitivity that 3, S is method,
that standard solution when concentration is C carries out average measurement, the mean value of the signal that meets with a response 3 times.To blank determination 11 times, try to achieve its standard deviation s
bmean value with signal
Experiment reagent: 0.01mol/L, the sodium nitroprusside solution of pH=12; 10% phosphoric acid; Sodium sulphide standard solution: 0.5 μ mol/L
Select the LED of 535nm, the length of ventilated membrane pipe is 3.5cm, and internal diameter is 2mm, tests at normal temperatures and pressures.
1) according to the method for step (1) in previous embodiment 1, carry out, repeat 11 times, obtain its standard deviation s
bmean value with signal
be respectively: 2.6x10
?4with 0.01594;
2) according to the method for the step in previous embodiment 1 (2), (3), (4), carry out, the standard solution that is 0.5 μ mol/L by concentration carries out average measurement three times, obtains the mean value of its signal
be 0.01915, by detection limit computing formula, calculate it and detect that to be limited to 0.12 μ mol/L be 0.0038mg/L.
3, interference test
Experiment reagent: 0.01mol/L, the sodium nitroprusside solution of pH=12; 10% phosphoric acid; Sodium sulphide standard solution: 25 μ mol/L.Sodium carbonate, sodium sulphite, reduced glutathione, L ?halfcystine, NaCl, KBr, CaCl
2, MgCl
2, NH
4the concentration of the interfering materials such as Cl is 2500 μ mol/L.
Experimentation: select the LED of 535nm, the length of ventilated membrane pipe is 3.5cm, and internal diameter is 2mm, tests at normal temperatures and pressures.
1) identical with the step (1) of previous embodiment 1;
2) identical with the step (2) of previous embodiment 1;
3) in reaction vessels 7, add 1.0ml2500 μ mol/L sodium carbonate respectively, sodium sulphite, reduced glutathione, L ?halfcystine, NaCl, KBr, CaCl
2, MgCl
2, NH
4cl solution, the condition of other conditions and above-mentioned sodium sulphide sample is consistent, by formula A
sample=lg (I
1/ I
t) calculate the absorbance of sulfide sample; Wherein: I
1the mean value of 30s light intensity before during for acid filling not; I
tfor the real-time light intensity value recording after acid filling.Result is as Fig. 4, and Fig. 4 is the absorbance figure of sodium sulphide and interfering ion, and wherein curve a is 25 μ mol/L sodium sulphide samples; Curve b～j is respectively: 2500 μ mol/L sodium carbonate, sodium sulphite, reduced glutathione, L ?halfcystine, NaCl, KBr, CaCl
2, MgCl
2, NH
4cl solution.
As shown in Figure 4, when other conditions are consistent, when the concentration of other materials is 100 times of sodium sulphide concentration, still do not disturb the detection of method of the present invention to sodium sulphide, so the method has good selectivity for the mensuration of sulfide.
In sum, method of the present invention can reach 0.004mg/L to the detectability of Sulfide in water, and the range of linearity can reach 0.016～1.6mg/L, when sodium carbonate, sodium sulphite, reduced glutathione, L ?halfcystine, Cl
?, Br
?, Ca
2+, Mg
2+, NH
4 +while being 100 times of sulphion concentration Deng the concentration of interfering material, still do not disturb the detection to sulfide.
Claims (4)
1. the pick-up unit of a long light path liquid sulfide, it is characterized in that: between power supply (1) and light source (3), by wire, be connected with rheostat (2), on the emitting light path of light source (3), be provided with lucifuge housing (5), lucifuge housing (5) is processed with respectively light hole and light hole on relative two side, the center line of light hole and light hole is on emergent light axis, in lucifuge housing (5), be provided with reaction vessels (7), top is provided with chemical feed pipe (8), the outlet of chemical feed pipe (8) extends in reaction vessels (7), in reaction vessels (7) along being radially provided with ventilated membrane pipe (9), one end of ventilated membrane pipe (9) is connected with incident optical (4) by feed tube (6), the other end is connected with outgoing optical fiber (11) by discharging tube (10), incident optical (4) is connected with the exit end of light source (3) through light hole, outgoing optical fiber (11) is connected with the input end of photoelectric commutator (12) through light hole, the output terminal of photoelectric commutator (12) is connected with data acquisition unit (13) by wire, data acquisition unit (13) is connected with computing machine (14) by wire,
The diameter of described ventilated membrane pipe (9) and lenth ratio are 1:10～50, and length is 2～10cm.
2. the pick-up unit of long light path liquid sulfide according to claim 1, it is characterized in that: described feed tube (6) and discharging tube (10) are T shape tubular construction, a port of feed tube (6) is connected with incident optical (4), another relative port is connected with ventilated membrane pipe (9), and the 3rd feed liquor port extends to lucifuge housing (5) outside; A port of discharging tube (10) is connected with ventilated membrane pipe (9), and another port on the other side is connected with outgoing optical fiber (11), and the 3rd fluid port extends to lucifuge housing (5) outside.
3. the pick-up unit of liquid medium sulphide content according to claim 1, is characterized in that: described light source is LED lamp, and wavelength is 500～600nm.
4. a detection method for long light path liquid sulfide, is characterized in that being comprised of following steps:
(1) to adding in reaction vessels (7) ultrapure water as adding the absorption liquid that pH is 9～13, concentration is 0.01～0.05mol/L in blank solution, ventilated membrane pipe (9), circulating direction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 500～600nm, light path is 2～10cm, logical optical cross-section diameter and light path ratio are 1:10～50, after 10～50s, in blank solution, add nonvolatile organic acids, outlet end at absorption liquid gathers light intensity, according to A
blank=lg (I
0/ I
t0) calculate blank absorbance;
I wherein
0the mean value of 10～50s light intensity before during for acid filling not; I
t0the real-time light intensity recording during second for t after acid filling;
(2) to adding in reaction vessels (7), in sulfide sample, ventilated membrane pipe (9), add the absorption liquid that pH is 9～13, concentration is 0.01～0.05mol/L, circulating direction from the liquid feeding end of absorption liquid along absorption liquid passes into the light that wavelength is 500～600nm, light path is 2～10cm, logical optical cross-section diameter and light path ratio are 1:10～50, after 10～50s, in sulfide sample, add nonvolatile organic acids, outlet end at absorption liquid gathers light intensity, according to A
sample=lg (I
1/ I
t1), calculate the absorbance of sulfide sample;
Wherein: I
1the mean value of 10～50s light intensity before during for acid filling not; I
t1the real-time light intensity recording second for t after acid filling;
(3), according to the sulfide sample absorbance of gained in the blank absorbency value of step (1) gained and step (2), calculate according to the following equation the clean absorbance A of sulfide sample
only:
A
only=A
sample-A
blank;
(4) with calibration curve method, calculate the concentration of institute's test sample product medium sulphide content;
Above-mentioned nonvolatile organic acids is sulfuric acid, phosphoric acid or trichloroacetic acid;
Above-mentioned absorption liquid is sodium nitroprusside solution or methyl green solution.
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| CN104316521A (en) * | 2014-10-27 | 2015-01-28 | 合肥卓越分析仪器有限责任公司 | Instrument for accurately determining sulfur in coal sample |
| CN105044090A (en) * | 2015-06-24 | 2015-11-11 | 陕西师范大学 | Sulfide detection method and device |
| CN110646599A (en) * | 2019-09-25 | 2020-01-03 | 福州大学 | Device for rapidly extracting hydrogen sulfide in cerebrospinal fluid and serum sample and using method thereof |
| CN114577793A (en) * | 2022-05-07 | 2022-06-03 | 北京大学 | Multi-scene hydrogen sulfide gas content online monitoring method and monitoring device |
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| US20080158563A1 (en) * | 2006-08-21 | 2008-07-03 | Pierre Simon Joseph Berini | Sensors |
| CN202814873U (en) * | 2012-06-07 | 2013-03-20 | 国家海洋局第一海洋研究所 | Detector for volatile sulphides in surface seawater and atmosphere |
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| CN103472022A (en) * | 2013-09-29 | 2013-12-25 | 山东省科学院海洋仪器仪表研究所 | Optical fiber sensor device used for on-line detection of concentration of sulfide in water and detection method |
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| US20080158563A1 (en) * | 2006-08-21 | 2008-07-03 | Pierre Simon Joseph Berini | Sensors |
| CN202814873U (en) * | 2012-06-07 | 2013-03-20 | 国家海洋局第一海洋研究所 | Detector for volatile sulphides in surface seawater and atmosphere |
| CN103389279A (en) * | 2013-08-06 | 2013-11-13 | 山东省科学院海洋仪器仪表研究所 | Device and method for online detection of concentration of sulfides in water by methylene blue spectrophotometric method |
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| CN104316521A (en) * | 2014-10-27 | 2015-01-28 | 合肥卓越分析仪器有限责任公司 | Instrument for accurately determining sulfur in coal sample |
| CN105044090A (en) * | 2015-06-24 | 2015-11-11 | 陕西师范大学 | Sulfide detection method and device |
| CN105044090B (en) * | 2015-06-24 | 2018-05-08 | 陕西师范大学 | A kind of detection method and device of sulfide |
| CN110646599A (en) * | 2019-09-25 | 2020-01-03 | 福州大学 | Device for rapidly extracting hydrogen sulfide in cerebrospinal fluid and serum sample and using method thereof |
| CN110646599B (en) * | 2019-09-25 | 2021-03-30 | 福州大学 | Device for rapidly extracting hydrogen sulfide in cerebrospinal fluid and serum sample and using method thereof |
| CN114577793A (en) * | 2022-05-07 | 2022-06-03 | 北京大学 | Multi-scene hydrogen sulfide gas content online monitoring method and monitoring device |
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