CN103389279B - The device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration - Google Patents
The device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration Download PDFInfo
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Abstract
The invention discloses a kind of device and method of sub-methyl blue spectrum analysis on-line checkingi water sample medium sulphide content concentration, described device comprises the serial components such as sample acidifying assembly, gas extraction assembly, solution absorbent assembly, gas supply assembly, colour developing and optical sensing module, present invention also offers the method utilizing described device to carry out on-line checkingi sulfide, measurement result is reliable and stable, testing process quick and precisely, favorable reproducibility, result is reliable and stable, testing process automatic operating can be realized, can long-time continuous real time on-line monitoring, use manpower and material resources sparingly.
Description
Technical field
The present invention relates to a kind of method detecting water sample medium sulphide content, particularly relate to the device and method that a kind of sub-methyl blue spectrum analysis detects Sulfide in Water concentration.
Background technology
Sulfide is one of important substance extensively existed in water quality, sulfide in water quality mainly contains two-part source: one is water Minerals itself containing sulfide, two is leathers, the waste water that gives off of papermaking, chemical industry, the industry such as printing and dyeing contains a large amount of sulfide.Sulfide is an important indicator of the important Testing index of water pollution, particularly bottom soil environment quality.The mensuration of water quality medium sulphide content is one of important indicator of environmental monitoring.Conventional detection method has photometry, chromatography, iodimetric titration, electrochemical method etc.The most frequently used in these methods is spectrophotometric method, and spectrophotometric method comprises again sub-methyl blue spectrum analysis, fluorimetry, gaseous state infrared spectrophotometer, gaseous state ultraviolet spectrophotometry, Flow Injection Spectrophotometry etc.Sub-methyl blue spectrum analysis wherein in spectroscopic methodology is the most classical analytical approach, is also the method for recommending in marine monitoring specification GB17378.4-2007.
The content of natural water body medium sulphide content is very low, utilizes existing instrument and equipment all directly can not measure it, has to pass through enrichment pre-treatment.Usually the analytical approach adopted both at home and abroad is after collection in worksite sample, carries out example enrichment process, then utilize spectrophotometric method, fluorescence method, vapor-phase chromatography etc. to detect in laboratory.Conventional enrichment method has: air-extraction, solid-phase microextraction, liquid-liquid extraction method, molecular sieve adsorption concentration method etc.Above each side fado number needs loaded down with trivial details treatment step, and operating cost is large, and detection time is long, is unsuitable for the automatic monitoring of continuous real-time online.
Therefore, develop a kind of apparatus and method of fast long-acting detection Sulfide in water content, the change of sulfide content can be detected by real-time online, become our urgent problem.
Summary of the invention
The object of the invention is to solve current water sample medium sulphide content cannot the deficiency of on-the-spot in-situ monitoring, provides a kind of device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The device of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration, this device comprises sample acidifying assembly, air lift assembly, solution absorbent assembly, gas supply assembly, colour developing and optical sensing module;
Described sample acidifying assembly comprises the 3rd T-valve, the 4th T-valve and the first peristaltic pump, and the outlet of described 3rd T-valve is connected with the normal opening of described 4th T-valve, and the outlet of described 4th T-valve is connected with the entrance of the first peristaltic pump;
Described air lift assembly comprises the second gas-liquid separation membrane be provided with above the second minipump, aeration tank, aeration tank, the temperature controller controlling aeration tank temperature, aeration tank is by the first normally closed cut-off valve effluent discharge, and described second micro vacuum delivery side of pump is connected into aeration tank by pipeline;
Described solution absorbent assembly comprises oxygen absorption pond, the first T-valve, the second T-valve, the first minipump and hydrogen sulfide absorption pond, described oxygen absorption pond is connected with the gas-liquid separation membrane above aeration tank and the normal opening of the first T-valve respectively by pipeline, the outlet of the second T-valve is connected with the entrance of the first minipump, is provided with the first gas-liquid separation membrane above described hydrogen sulfide absorption pond; First micro vacuum delivery side of pump is connected in hydrogen sulfide absorption pond by pipeline;
Described gas supply assembly comprises carrier gas bottle and trimmer valve;
Described colour developing and optical sensing module comprise the 5th T-valve, the 6th T-valve, reaction coil pipe, flow cell, the second peristaltic pump; The normal opening of described 5th T-valve is connected with the second normally closed cut-off valve, and the normal opening of the 6th T-valve is connected with the outlet of the 5th T-valve, and the 6th T-valve outlet is connected with flow cell entrance through reaction coil pipe, and flow cell outlet is connected with the second peristaltic pump; Described flow cell is connected with photoelectric gathering apparatus.
Further, described solution absorbent assembly is also connected with gas buffer bag and drying tube between the first T-valve and the second T-valve.
Further, described gas supply assembly is connected with flow controller after trimmer valve.
Further, the second normally closed cut-off valve is also connected with between described hydrogen sulfide absorption pond and the 5th T-valve.
Present invention also offers the method for the device on-line checkingi water sample medium sulphide content concentration described in utilization, it comprises the following steps:
(1) open carrier gas bottle, open the first T-valve and the first minipump, pass into the inert gas needing consumption, close the first T-valve and the first minipump;
(2) open the first peristaltic pump, pump into water body example to be measured to aeration tank, unlatching the 3rd T-valve pumps into again goes back original reagent to aeration tank, closes the 3rd T-valve, continues to pump into water body example, and fully original reagent and water body example are gone back in mixing; Open the 4th T-valve, then pump into acid reagent to aeration tank, close the 4th T-valve, continue to pump into water body example, fully mixing acid reagent and water body example; Opening temperature controller keeps temperature in aeration tank at 50-60 DEG C, and the sulfide in water sample, in acid medium and under the condition of heating, is converted into volatile hydrogen sulfide gas;
(3) open the second minipump and pump into inert gas, the sulfuretted hydrogen of generation is purged air lift by inert gas from water body example, enter oxygen absorption pond through the second gas-liquid separation membrane, remove the oxygen existed in gas, open the first normally closed cut-off valve with the water body waste liquid after emptying aeration;
(4) the second T-valve and the first minipump is opened, pump into absorption reagent to hydrogen sulfide absorption pond, the first minipump is kept to be in opening, close the second T-valve, volatility sulfuretted hydrogen and inert gas is made to enter hydrogen sulfide absorption pond after removing oxygen and water vapor, sulfuretted hydrogen in gas, after hydrogen sulfide absorption pond absorbs, transfers the absorption reagent containing sulphion to; (5) close the first minipump, open the second peristaltic pump and the second normally closed cut-off valve, pump into described absorption reagent containing sulphion to reaction coil pipe, open the 5th T-valve, pump into catalyzer to reaction coil pipe, open the 6th T-valve, pump into chromogenic reagent to reaction coil pipe; Sulphion in absorption reagent, under acid condition and ferric ion exist, reacts with P-aminodimethylaniline hydrochloride and generates methylene blue; Mixed liquor containing methylene blue circulates pond, utilizes photoelectric gathering apparatus collection measure the light intensity of described flow cell and calculate absorbance; The light absorption value of mensuration and standard absorbance curve are quantitatively converted, calculates the concentration of sulfide.
Further, containing absorption reagent in described hydrogen sulfide absorption pond, described absorption reagent is zinc acetate-aqueous sodium acetate solution, and it consists of: the mass percent of zinc acetate is 5 ~ 10%, and the mass percent of sodium acetate is 1 ~ 2%.
Further, to go back original reagent described in be mass percent be 10 ~ 20% ascorbic acid solution; Described acid reagent to be mass percent be 10 ~ 30% hydrochloric acid.
Further, described catalyzer is acid iron sulfate aqueous ammonium, consisting of of catalyzer: the mass percent of ammonium ferric sulfate is 10 ~ 20%, and the concentration of sulfuric acid is 0.5 ~ 1mol/L.
Further, chromogenic reagent is P-aminodimethylaniline hydrochloride aqueous solution, consisting of in chromogenic reagent: the mass percent of P-aminodimethylaniline hydrochloride is 0.1 ~ 0.2%, and the concentration of sulfuric acid is 3 ~ 5mol/L.
Further, described inert gas is the nitrogen or argon gas that top grade is pure, and in drying tube, solid is anhydrous calcium chloride, and in oxygen absorption pond, solution is saturated sodium sulfite aqueous solution.
Compared with prior art, advantage of the present invention and good effect are: the method for coupling air lift enrichment in the present invention, fluorimetry and flow injection, have developed a kind of can on-the-spot, fast, the method for on-line checkingi water quality medium sulphide content and supporting device, enormously simplify operation steps.Sulfide in water body, under the condition that acid medium also heats, is converted into volatile hydrogen sulfide gas; Adopt inertia high-purity carrier gas that the sulfuretted hydrogen of generation is purged air lift from water body example, after oxygen absorption pond and drying tube remove oxygen and water vapor respectively, enter hydrogen sulfide absorption pond; Hydrogen sulfide gas, after absorption cell is absorbed by zinc acetate-aqueous sodium acetate solution, transfers sulphion to; Sulphion in absorption reagent, under acid condition and ferric ion exist, reacts with P-aminodimethylaniline and generates methylene blue; The methylene blue that reaction generates circulates behind pond, measures its light intensity and calculate absorbance at 650nm wavelength; Absorbance, through quantitatively converting with standard absorbance curve, calculates the content of sulfide, thus realizes the detection to Sulfide in Water.
The present invention utilizes sample acidifying assembly, air lift assembly, solution absorbent assembly, gas supply assembly, colour developing and optical sensing module, form the pick-up unit of the system integration, measurement result is reliable and stable, testing process quick and precisely, favorable reproducibility, result is reliable and stable, can realize testing process automatic operating, can long-time continuous real time on-line monitoring, use manpower and material resources sparingly.
After reading the specific embodiment of the present invention by reference to the accompanying drawings, the other features and advantages of the invention will become clearly.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration of the present invention, is also the process chart of Sulfide in Water analytical approach of the present invention.
MP1-minipump; MP2-minipump; PP1-peristaltic pump; PP2-peristaltic pump;
V1-T-valve; V2-T-valve; V3-T-valve; V4-T-valve; V5-T-valve; V6-T-valve;
M1-gas-liquid separation membrane; M2-gas-liquid separation membrane; C1-normally closed cut-off valve; C2-normally closed cut-off valve;
1-carrier gas bottle; 2-trimmer valve; 3-flow controller; 4-gas buffer bag; 5-drying tube; 6-hydrogen sulfide absorption pond; 7-aeration tank; 8-temperature controller; 9-oxygen absorption pond; 10-reacts coil pipe; 11-fluorescence flow cell; 12-photoelectric gathering apparatus;
R1-is original reagent also; R2-acid reagent; R3-absorption reagent; R4-catalyzer; R5-chromogenic reagent; S-water sample; WS1-waste liquid; WS2-waste liquid.
Embodiment
Below in conjunction with the drawings and specific embodiments, the device of detection Sulfide in Water of the present invention and described sulfide automatic analysis method are described in further detail.
Embodiment 1
The structure of Sulfide in Water automatic analysing apparatus of the present invention as shown in Figure 1.The device of on-line checkingi water sample medium sulphide content concentration of the present invention comprises sample acidifying assembly, air lift assembly, solution absorbent assembly, gas supply assembly, colour developing and optical sensing module.
Peristaltic pump PP1, PP2 of the present invention are commercially available 6 rotor pulse pumps, pump discharge 1 ~ 100ml/min; Minipump MP1, MP2 are commercially available pump, pump discharge 10 ~ 1000ml/min; T-valve V1, V2, V3, V4, V5, V6 are commercially available two-bit triplet solenoid valve, and inner core is made up of acid and alkali-resistance materials such as PEEK.Three-way solenoid valve has an outlet, two imports, and import is divided into normal opening and normally closed port, connects, working pressure 2 ~ 3 × 10 with flexible pipes such as fluorine sebific ducts
5pa.Normally closed cut-off valve C1, C2 are solenoid valve, and material is PEEK, working pressure 2 ~ 3 × 10
5pa.Flexible pipe is commercially available fluorine sebific duct, and internal diameter is 2-5mm.
Described sample acidifying assembly comprises the 3rd T-valve (i.e. T-valve V3), the 4th T-valve (i.e. T-valve V4) and the first peristaltic pump (i.e. peristaltic pump PP1), the normal opening of described T-valve V3 is used for water sample S sample introduction to be measured, normally closed port is used for going back original reagent R1 sample introduction, the outlet of described T-valve V3 is connected with the normal opening of described T-valve V4, and T-valve V4 normally closed port is used for acid reagent R2 sample introduction.Described T-valve V4 outlet utilizes flexible pipe to be connected with peristaltic pump PP1 entrance.Peristaltic pump PP1 outlet utilizes flexible pipe, PEEK joint, polypropylene packing ring to be connected with aeration tank 7.
Described air lift assembly comprises the second gas-liquid separation membrane (i.e. gas-liquid separation membrane M2), the temperature controller 8 that are provided with above the second minipump (i.e. minipump MP2), aeration tank 7, aeration tank, and aeration tank 7 is by the first normally closed cut-off valve (i.e. normally closed cut-off valve C1) effluent discharge WS1.Aeration tank 7 is designed to glass rectangular parallelepiped, and aeration tank upper surface is provided with gas-liquid separation membrane M2, is provided with temperature controller 8 outside aeration tank 7, containing temperature probe in temperature controller.Aeration tank 7 bottom interface is connected with normally closed cut-off valve C1, emptying for water sample waste liquid W S1.Aeration tank 7 bottom interface exports with minipump MP2 simultaneously and is connected, for receiving inert gas carrier needed for aeration tank 7.
Described solution absorbent assembly comprises oxygen absorption pond 9, first T-valve (T-valve V1), the second T-valve (T-valve V2), the first minipump (minipump MP1) and hydrogen sulfide absorption pond 6, described oxygen absorption pond 9 is connected with aeration tank 7 and the normal opening of T-valve V1 respectively by pipeline, the outlet of T-valve V2 is connected with the entrance of minipump MP1, is provided with the first gas-liquid separation membrane (gas-liquid separation membrane M1) above described hydrogen sulfide absorption pond; The outlet of minipump MP1 is connected in hydrogen sulfide absorption pond by pipeline, and the entrance of minipump MP2 is connected with the gas-liquid separation membrane M1 upper outlet in hydrogen sulfide absorption pond by pipeline.Gas-liquid separation membrane M2 outlet to be connected with oxygen absorption pond 9 entrance by flexible pipe and to be deep into bottom oxygen absorption pond.The outlet in oxygen absorption pond 9 is located at and absorbs more than liquid level, is connected with the normal opening of T-valve V1 by flexible pipe.T-valve V1 normally closed port is connected with flowmeter 3, and carrier gas bottle 1 is connected with flowmeter 3 by trimmer valve 2, and described T-valve V1 is used for quantitatively supplementing inert carrier gas.T-valve V2 normally closed port is used for absorption reagent R3 sample introduction, and outlet is connected with minipump MP1 entrance.Minipump MP1 outlet utilizes flexible pipe, PEEK joint, polypropylene packing ring to be connected with hydrogen sulfide absorption pond 6 entrance.Hydrogen sulfide absorption pond 6 is designed to glass rectangular parallelepiped, and upper surface has gas-liquid separation membrane M1, is connected with minipump MP2.Hydrogen sulfide absorption pond 6 is connected with normally closed cut-off valve C2 entrance.
Described gas supply assembly comprises carrier gas bottle 1 and trimmer valve 2; Flow controller 3 can also be comprised.
Described colour developing and optical sensing module comprise connected by pipeline successively the 5th T-valve (i.e. T-valve V5), the 6th T-valve (i.e. T-valve V6), reaction coil pipe 10, flow cell 11, second peristaltic pump (peristaltic pump PP2); Described peristaltic pump PP2 is also connected with second normally closed cut-off valve (normally closed cut-off valve C2) of effluent discharge WS2; The normal opening of T-valve V5 exports with normally closed cut-off valve C2 and is connected, and T-valve V5 normally closed port is used for catalyzer R4 sample introduction; The normal opening of T-valve V6 exports with T-valve V5 and is connected, and T-valve V6 normally closed port is used for chromogenic reagent R5 sample introduction.T-valve V6 exports and is connected with reaction coil pipe 10 entrance.Described reaction coil pipe 10 is by the sped structure of polyfluortetraethylene pipe coiling.Flow cell 11 entrance exports with reaction coil pipe 10 and is connected, and outlet is connected with peristaltic pump PP2 entrance.Peristaltic pump PP2 exports and is used for the emptying of waste liquid W S2.Described flow cell 10 is Z-type flow cell, is provided with fluid intake, fluid egress point and light entrance port, optical emission exit totally four interfaces.Wavelength is that the LED of 650nm enters light entrance port after coupling fiber, conduction, and the light that optical emission exit sends utilizes photoelectric gathering apparatus 12 to measure its light intensity after fiber optic conduction, coupling.Utilize the light intensity measured to calculate absorbance, and quantitatively convert with standard absorbance curve, calculate the concentration of sulfide, thus realize the mensuration of Sulfide in Water concentration.
Described solution absorbent assembly also comprises gas buffer bag 4 and drying tube 5.The outlet of T-valve V1 is connected with gas buffer bag 4, and the outlet of gas buffer bag 4 is connected with drying tube 5.Drying tube 5 utilizes flexible pipe outlet to be connected with the normal opening of T-valve V2.
Needed first to prepare related solution before carrying out test sulfide concentration.The standard specimen of preparation needed for test analysis and solution as follows:
1, absorption reagent is prepared
Take 50 g zinc acetate [Zn (CH
3cOO)
22H
2o] and 12.5g sodium acetate [CH
3cOONaH
2o] be dissolved in a small amount of water, be diluted to 1L, mixing.
2, original reagent is gone back in preparation
Take 50 g ascorbic acid [C
6h
8o
6] be dissolved in 250ml water.
3, acid reagent is prepared
Measure 100mL hydrochloric acid (HCl, ρ=1.19g/mL) slowly to join in 100ml water, be cooled to room temperature.
4, catalyzer is prepared
Take 25 g ammonium ferric sulfate [Fe (NH
4) (SO
4)
212H
2o] in 250ml beaker, add in 100ml water, slowly add concentrated sulphuric acid 5ml [H
2sO
4, ρ=1.84g/mL], be diluted with water to 200ml after cooling.
5, chromogenic reagent is prepared
Take 1 g P-aminodimethylaniline hydrochloride [NH
2c
6h
4n (CH
3)
22HCl] in 700ml water, slowly add concentrated sulphuric acid 200ml [H
2sO
4, ρ=1.84g/mL], be diluted with water to 1000ml after cooling.
The method utilizing device of the present invention to carry out on-line checkingi water sample medium sulphide content concentration comprises the following steps:
1, open the trimmer valve 2 of carrier gas bottle 1, open T-valve V1, the inert gas in carrier gas bottle 1 is through trimmer valve 2, flowmeter 3 admission passage and gas bumping bag 4.Continue to pass into inert gas 20min, the gas flow of control flow check amount controller 3 is 500 ml/min.Close T-valve V1 and trimmer valve 2.
2, open peristaltic pump PP1, pump into water body example S to be measured to aeration tank 7, continue to pump into 20min, maintenance pump speed is 50ml/min.Keep peristaltic pump PP1 to be in opening, adjustment pump speed is 5ml/min, opens T-valve V3, pumps into and go back original reagent R1 ascorbic acid solution 1min to aeration tank 7; Close T-valve V3, maintenance pump speed is 5ml/min, pumps into water body 2min to aeration tank 7, and fully original reagent and water body example are gone back in mixing.
Open T-valve V4, maintenance pump speed is 5ml/min, pumps into acid reagent R2 and continues 2min to aeration tank 7; Close T-valve V4, maintenance pump speed is 5ml/min, pumps into water body 2min to aeration tank 7, fully mixing acid reagent and water body example; And open temperature controller 8, the temperature in maintenance aeration tank 7 is at 50-60 DEG C.Sulfide in water sample, in acid medium and under the condition of heating, is converted into volatile hydrogen sulfide gas.
3, open minipump MP2, pump into inert gas (inert gas storage be filled with is in gas buffer bag).The sulfuretted hydrogen of generation is purged air lift by inert carrier gas from water body example, enters oxygen absorption pond 9 through gas-liquid separation membrane M2, removes the oxygen that may exist in gas.Open normally closed cut-off valve C1, the water body waste liquid W S1 after emptying aeration.
4, open T-valve V2 and open minipump MP1, maintenance pump speed is 5ml/min, pumps into absorption reagent 1min to hydrogen sulfide absorption pond 6.Keep minipump MP1 to be in opening, close T-valve V2, pump into volatility sulfuretted hydrogen and inert gas.Volatility sulfuretted hydrogen and inert gas are removed oxygen through oxygen absorption pond 9 and are entered gas buffer bag 4, and drying pipe 5 enters hydrogen sulfide absorption pond 6 after removing water vapor.Sulfuretted hydrogen in gas, after hydrogen sulfide absorption pond 6 absorbs, transfers the absorption reagent containing sulphion to.
5, close minipump MP1, open peristaltic pump PP2, open normally closed cut-off valve C2, maintenance pump speed is 1ml/min, pumps into absorption reagent 2min to reaction coil pipe 10.Open T-valve V5, pump into catalyzer 0.5min to reaction coil pipe; Close T-valve V5, continue to pump into absorption reagent 1min to reaction coil pipe.Open T-valve V6, pump into chromogenic reagent R5 2min to reaction coil pipe; Close T-valve V6, continue to pump into absorption reagent 2min to reaction coil pipe.
Sulphion in absorption reagent, under acid condition and ferric ion exist, reacts with P-aminodimethylaniline hydrochloride and generates methylene blue; After mixed liquor containing methylene blue enters Z-type flow cell, wavelength is that the LED of 650nm enters light entrance port after coupling fiber, conduction, and the light that optical emission exit sends utilizes photoelectric gathering apparatus 12 to measure its light intensity after fiber optic conduction, coupling; Utilize the light intensity measured to calculate absorbance, and quantitatively convert with standard absorbance curve, calculate the concentration of sulfide, thus realize the mensuration of Sulfide in Water concentration.After mensuration completes, open peristaltic pump PP2, open normally closed cut-off valve C2, remaining absorption reagent is effluent discharge WS1 after three-way solenoid valve V5, three-way solenoid valve V6, reaction coil pipe 10, fluorescence flow cell 11.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (10)
1. the device of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration, is characterized in that, this device comprises sample acidifying assembly, air lift assembly, solution absorbent assembly, gas supply assembly, colour developing and optical sensing module;
Described sample acidifying assembly comprises the 3rd T-valve, the 4th T-valve and the first peristaltic pump, and the outlet of described 3rd T-valve is connected with the normal opening of described 4th T-valve, and the outlet of described 4th T-valve is connected with the entrance of the first peristaltic pump;
Described air lift assembly comprises the second gas-liquid separation membrane be provided with above the second minipump, aeration tank, aeration tank, the temperature controller controlling aeration tank temperature, aeration tank is by the first normally closed cut-off valve effluent discharge, and described second micro vacuum delivery side of pump is connected into aeration tank by pipeline;
Described solution absorbent assembly comprises oxygen absorption pond, the first T-valve, the second T-valve, the first minipump and hydrogen sulfide absorption pond, described oxygen absorption pond is connected with the gas-liquid separation membrane above aeration tank and the normal opening of the first T-valve respectively by pipeline, the outlet of the second T-valve is connected with the entrance of the first minipump, is provided with the first gas-liquid separation membrane above described hydrogen sulfide absorption pond; First micro vacuum delivery side of pump is connected in hydrogen sulfide absorption pond by pipeline;
Described gas supply assembly comprises carrier gas bottle and trimmer valve;
Described colour developing and optical sensing module comprise the 5th T-valve, the 6th T-valve, reaction coil pipe, flow cell, the second peristaltic pump; The normal opening of described 5th T-valve is connected with the second normally closed cut-off valve, and the normal opening of the 6th T-valve is connected with the outlet of the 5th T-valve, and the 6th T-valve outlet is connected with flow cell entrance through reaction coil pipe, and flow cell outlet is connected with the second peristaltic pump; Described flow cell is connected with photoelectric gathering apparatus.
2., according to the device of the sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration described in claim 1, it is characterized in that: described solution absorbent assembly is also connected with gas buffer bag and drying tube between the first T-valve and the second T-valve.
3. the device of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration according to claim 1, is characterized in that: described gas supply assembly is connected with flow controller after trimmer valve.
4. the device of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration according to claim 1, is characterized in that: be also connected with the second normally closed cut-off valve between described hydrogen sulfide absorption pond and the 5th T-valve.
5. utilize the method for the device on-line checkingi water sample medium sulphide content concentration described in any one of claim 1-4, it is characterized in that it comprises the following steps:
(1) open carrier gas bottle, open the first T-valve and the first minipump, pass into the inert gas needing consumption, close the first T-valve and the first minipump;
(2) open the first peristaltic pump, pump into water body example to be measured to aeration tank, unlatching the 3rd T-valve pumps into again goes back original reagent to aeration tank, closes the 3rd T-valve, continues to pump into water body example, and fully original reagent and water body example are gone back in mixing; Open the 4th T-valve, then pump into acid reagent to aeration tank, close the 4th T-valve, continue to pump into water body example, fully mixing acid reagent and water body example; Opening temperature controller keeps temperature in aeration tank at 50-60 DEG C, and the sulfide in water sample, in acid medium and under the condition of heating, is converted into volatile hydrogen sulfide gas;
(3) open the second minipump and pump into inert gas, the sulfuretted hydrogen of generation is purged air lift by inert gas from water body example, enter oxygen absorption pond through the second gas-liquid separation membrane, remove the oxygen existed in gas, open the first normally closed cut-off valve with the water body waste liquid after emptying aeration; (4) the second T-valve and the first minipump is opened, pump into absorption reagent to hydrogen sulfide absorption pond, described first minipump is kept to be in opening, close the second T-valve, volatility sulfuretted hydrogen and inert gas is made to enter hydrogen sulfide absorption pond after removing oxygen and water vapor, sulfuretted hydrogen in gas, after hydrogen sulfide absorption pond absorbs, transfers the absorption reagent containing sulphion to;
(5) close the first minipump, open the second peristaltic pump and the second normally closed cut-off valve, pump into absorption reagent containing sulphion to reaction coil pipe, open the 5th T-valve, pump into catalyzer to reaction coil pipe, open the 6th T-valve, pump into chromogenic reagent to reaction coil pipe; Sulphion in absorption reagent, under acid condition and ferric ion exist, reacts with P-aminodimethylaniline hydrochloride and generates methylene blue; Mixed liquor containing methylene blue circulates pond, utilizes photoelectric gathering apparatus collection measure the light intensity of described flow cell and calculate absorbance; The light absorption value of mensuration and standard absorbance curve are quantitatively converted, calculates the concentration of sulfide.
6. according to the method for the on-line checkingi water sample medium sulphide content concentration described in claim 5, it is characterized in that: containing absorption reagent in described hydrogen sulfide absorption pond, described absorption reagent is zinc acetate-aqueous sodium acetate solution, it consists of: the mass percent of zinc acetate is 5 ~ 10%, and the mass percent of sodium acetate is 1 ~ 2%.
7., according to the method for the on-line checkingi water sample medium sulphide content concentration described in claim 5, it is characterized in that: described in go back original reagent be mass percent be 10 ~ 20% ascorbic acid solution; Described acid reagent to be mass percent be 10 ~ 30% hydrochloric acid.
8. according to the method for the on-line checkingi water sample medium sulphide content concentration described in claim 5, it is characterized in that: described catalyzer is acid iron sulfate aqueous ammonium, consisting of of catalyzer: the mass percent of ammonium ferric sulfate is 10 ~ 20%, the concentration of sulfuric acid is 0.5 ~ 1mol/L.
9. according to the method for the on-line checkingi water sample medium sulphide content concentration described in claim 5, it is characterized in that: chromogenic reagent is P-aminodimethylaniline hydrochloride aqueous solution, consisting of in chromogenic reagent: the mass percent of P-aminodimethylaniline hydrochloride is 0.1 ~ 0.2%, the concentration of sulfuric acid is 3 ~ 5mol/L.
10., according to the method for the on-line checkingi water sample medium sulphide content concentration described in claim 5, it is characterized in that: described inert gas is the nitrogen or argon gas that top grade is pure, in oxygen absorption pond, solution is saturated sodium sulfite aqueous solution.
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|---|---|---|---|
| CN201310339352.5A CN103389279B (en) | 2013-08-06 | 2013-08-06 | The device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration |
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| CN201310339352.5A CN103389279B (en) | 2013-08-06 | 2013-08-06 | The device and method of sub-methyl blue spectrum analysis on-line checkingi water quality medium sulphide content concentration |
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| CN103389279A CN103389279A (en) | 2013-11-13 |
| CN103389279B true CN103389279B (en) | 2015-08-12 |
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| CN103983590B (en) * | 2014-05-30 | 2016-11-02 | 陕西师范大学 | A kind of detection device and method of long light path liquid sulfide |
| CN104949968A (en) * | 2015-06-10 | 2015-09-30 | 苏州东辰林达检测技术有限公司 | Detection reagent for hydrogen sulfide in beer and detection method adopting detection reagent |
| CN105021592A (en) * | 2015-06-19 | 2015-11-04 | 上海人本集团有限公司 | Measurement method for sulfide content in bearing production sewage |
| CN104965094B (en) * | 2015-07-03 | 2017-05-10 | 贵州省环境科学研究设计院 | Automatic release and absorption device for liquid-solid sample sulfides |
| CN107290553B (en) * | 2015-07-15 | 2019-05-03 | 厦门市吉龙德环境工程有限公司 | Dissolvable sulfide analysis method in a kind of water sample |
| CN105424630B (en) * | 2015-12-22 | 2018-09-18 | 湖南普泰尔环境股份有限公司 | A method of detection deodorant is to hydrogen sulfide removal rate |
| CN108941600A (en) * | 2018-07-09 | 2018-12-07 | 宁波中科科创新能源科技有限公司 | Nanometer platinum colloid preparation method and hydrogen molecule concentration indicator preparation method |
| CN111175462A (en) * | 2020-01-10 | 2020-05-19 | 南京公诚节能新材料研究院有限公司 | COD water quality on-line automatic monitor |
| CN113670908A (en) * | 2021-08-16 | 2021-11-19 | 杭州绿洁环境科技股份有限公司 | Sulfide analyzer and analysis method |
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| JPS5551353A (en) * | 1978-10-11 | 1980-04-15 | Nippon Steel Corp | Method and device for automatic analysis of ultra-microamount sulfur |
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| CN101788493A (en) * | 2010-01-19 | 2010-07-28 | 成都海兰天澄科技有限公司 | Method for testing ammonia nitrogen in water |
| CN102466636A (en) * | 2010-11-09 | 2012-05-23 | 国家海洋局第一海洋研究所 | Device for detecting marine volatile sulfur compounds with ultraviolet fluorescence method and manufacture method of device |
| 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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