CN104977265A - Analyzer and analytical method for soluble sulfides in water sample - Google Patents
Analyzer and analytical method for soluble sulfides in water sample Download PDFInfo
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- CN104977265A CN104977265A CN201510415448.4A CN201510415448A CN104977265A CN 104977265 A CN104977265 A CN 104977265A CN 201510415448 A CN201510415448 A CN 201510415448A CN 104977265 A CN104977265 A CN 104977265A
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- peristaltic pump
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000004458 analytical method Methods 0.000 title claims abstract description 10
- 150000003568 thioethers Chemical class 0.000 title abstract description 9
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000005259 measurement Methods 0.000 claims abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 32
- 238000002835 absorbance Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 230000008676 import Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000013459 approach Methods 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 claims description 4
- KTWNIUBGGFBRKH-UHFFFAOYSA-N [4-(dimethylamino)phenyl]azanium;chloride Chemical compound Cl.CN(C)C1=CC=C(N)C=C1 KTWNIUBGGFBRKH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000010985 leather Substances 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- 238000012937 correction Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000005477 standard model Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses an analyzer for soluble sulfides. The analyzer is characterized by comprising first to seventh three-way valves, an air pump, a peristaltic pump, a mixing tube, a cuvette, a stripping tube, and a T-shaped three-way device. The bottom of the mixing tube is provided with an inlet, and the top and one side of the mixing tube are provided with outlets, respectively. The bottom of the stripping tube is provided with a liquid inlet, and the top of the stripping tube is provided with a liquid outlet and an air outlet. The invention further comprises an analytical method for soluble sulfides in a water sample by adopting the analyzer. When the analyzer for soluble sulfides in the water sample is used for analyzing the soluble sulfides in the water sample, the soluble sulfides in the water sample can be accurately measured, and especially the soluble sulfides in a water sample (such as leather waste water and petrochemical waste water) with relatively complex components or chromaticity itself can be accurately measured. The analyzer has advantages of automatic detection and high measurement accuracy.
Description
Technical field
The present invention relates to sulfide analysis field, particularly dissolvable sulfide analyser and analytical approach in a kind of water sample.
Background technology
The sulfide existed in water, comprises deliquescent H
2s, HS
-, S
2-, acid soluble metal sulfide, and insoluble sulfide and organic sulfide.At present, in water sample, the inspection method of the routine of dissolvable sulfide is directly reacted, sulphion in sample and P-aminodimethylaniline in acid medium, at Fe
3+generate blue MBD under catalytic action, color depth is directly proportional to sulphion concentration in water.Analyser measures the ABS value of reaction of formation material in certain wave strong point, and calculates the concentration of sample according to the correction data be stored in analyser.The method of this routine cannot detect that composition is more complicated or itself is with the water sample of colourity, as leather waste water, and petrochemical wastewater etc.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide and a kind ofly may be used for detecting that composition is more complicated or itself is with the analyser of dissolvable sulfide in the water sample of colourity and analytical approach.
For achieving the above object, technical scheme proposed by the invention is: a kind of dissolvable sulfide analyser, is characterized in that: comprise the first to the 17 T-valve, air pump, peristaltic pump, mixing tube, colorimetric pool, blow-off tube, T-shaped threeway; Be provided with an import bottom described fixed tube, top and sidepiece are respectively provided with an outlet, are provided with a liquid-inlet bottom described blow-off tube, and top is provided with a liquid outlet and a gas vent;
The first described T-valve normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, and common port connects the normal-closed end of the second T-valve, and the second T-valve Chang Kaiduan connects the 3rd T-valve Chang Kaiduan, and common port connects the 4th T-valve Chang Kaiduan; 3rd T-valve normal-closed end connects waste solution channel, and common port connects colorimetric pool outlet; 4th T-valve normal-closed end connects iron chloride pipeline, and common port connects the 5th T-valve Chang Kaiduan; 5th T-valve normal-closed end connects N, N-dimethyl-p-phenylenediamine hydrochloride pipeline, and common port connects the 6th T-valve Chang Kaiduan; 6th T-valve normal-closed end connects NaOH pipeline, and common port connects the 7th T-valve Chang Kaiduan;
The 9th described T-valve normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, common port connects the tenth T-valve Chang Kaiduan; Tenth T-valve normal-closed end connects sampling pipe, common port connects the 11 T-valve Chang Kaiduan; 11 T-valve normal-closed end connects mark liquid pipeline, common port connects the 12 T-valve Chang Kaiduan; 12 T-valve normal-closed end connects waste solution channel, and common port connects the 13 T-valve Chang Kaiduan; 13 T-valve Chang Kaiduan connects zinc sulfate pipeline, and common port connects the 14 T-valve Chang Kaiduan; 14 T-valve normal-closed end connects NaOH pipeline, and common port connects the 15 T-valve Chang Kaiduan; 15 T-valve normal-closed end connects sulfuric acid and hydrogen peroxide solution pipeline, and common port connects the 7th T-valve normal-closed end;
The 7th described T-valve common port connects peristaltic pump; 8th T-valve normal-closed end connecting T-shaped threeway first passage, common port connects peristaltic pump, Chang Kaiduan connects the 16 T-valve Chang Kaiduan; 16 T-valve normal-closed end connects blow-off tube gas vent, and Chang Kaiduan connects mixing tube import; Mixing tube lateral outlet connects colorimetric pool import, and top exit connects the 17 T-valve normal-closed end; Described T-shaped threeway second channel connects air pump, third channel connects blow-off tube; The 17 described T-valve Chang Kaiduan connects blow-off tube liquid outlet, and the pipeline of the 17 T-valve connection blow-off tube liquid outlet extends to the quantitative liquid level position place in blow-off tube, and the 17 T-valve common port connects waste solution channel.
The present invention also comprises dissolvable sulfide analytical approach in a kind of water sample, it is characterized in that adopting dissolvable sulfide analyser in above-mentioned water sample to carry out dissolvable sulfide analysis in water sample.
Further, the entire protocol adopting dissolvable sulfide analyser of the present invention to carry out dissolvable sulfide analysis in water is:
Step 1: after instrument starts measurement, first the absorbing liquid carrying out sulfide suction line is taken into, first T-valve, second T-valve, 3rd T-valve action, wherein the second T-valve and the 3rd T-valve action simultaneously (i.e. energising simultaneously or simultaneously no power), peristaltic pump rotates forward, pure water is taken into the first T-valve from pure water pipeline, according to the opening and closing rule of valve, through the first T-valve after pure water enters from the first T-valve, second T-valve, 4th T-valve, 5th T-valve, 6th T-valve, 7th T-valve, 8th T-valve, enter from the lower end of mixing tube after 16 T-valve, liquid level flows out through colorimetric pool from this outlet after arriving the outlet of mixing tube upper lateral, final arrival the 3rd T-valve, discharge from the waste solution channel of the 3rd T-valve, then action is stopped after guaranteeing to be full of pure water in suction line,
Step 2: the 6th T-valve and the 3rd T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in suction line, and unnecessary liquid is drained from the waste solution channel overflow of the 3rd T-valve; The all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to abundant mixing;
Step 3: after completing the absorbing liquid preliminary work of suction line, 12 T-valve, the 7th T-valve, the 8th T-valve action, wherein the 7th T-valve and the 8th T-valve action simultaneously (i.e. energising simultaneously or simultaneously no power), play the effect switching pipeline; Peristaltic pump reverses, the pure water stayed after cleaning in blow-off tube is carried out emptying: manage interior pure water through pipe lower end to T-shaped threeway, again through the 8th T-valve, the 7th T-valve, the 15 T-valve, the 14 T-valve, the 13 T-valve, the 12 T-valve, discharge from the sewer pipe of the normal-closed end of the 12 T-valve;
Step 4: the tenth T-valve, the 7th T-valve, the 8th T-valve action, peristaltic pump rotates forward; Water sample is taken into from stopple coupon, according to the opening and closing rule of valve, after the tenth T-valve, the 11 T-valve, the 12 T-valve, the 13 T-valve, the 14 T-valve, the 15 T-valve, the 7th T-valve, the 8th T-valve, blow-off tube is arrived after water sample enters from stopple coupon, along with water sample amount increases, after water sample liquid level arrival the 7th T-valve Chang Kaiduan stretches into the surface of contact of the pipeline of blow-off tube, unnecessary water is just outwards drained from this pipeline, reaches quantitative object with this; Closedown the tenth T-valve after quantitative sample injection completes, the 7th T-valve, the 8th T-valve and peristaltic pump still keep action, and air enters from the 6th T-valve draft tube, is all pushed in blow-off tube by the water sample in pipeline, stops everything afterwards;
Step 5: the 14 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in blow-off tube from the normal-closed end of the 14 T-valve;
Step 6: close the 16 T-valve, 9th T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump rotates forward, pure water from pure water pipeline join blow-off tube, quantitatively enter rear closedown the 9th T-valve, other valves and peristaltic pump keep action, and now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mix rear peristaltic pump and stop;
Step 7: the 13 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, solution of zinc sulfate is quantitatively joined in blow-off tube from the normal-closed end of the 13 T-valve, now forms White Flocculus; Close the 13 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve stay open simultaneously, peristaltic pump rotates forward, and pure water joins blow-off tube from the normal-closed end of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 8: the 15 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sulfuric acid and hydrogen peroxide solution (H
2sO
42N+20%H
2o
2) quantitatively joined in blow-off tube from the normal-closed end of the 15 T-valve, now White Flocculus disappears, and sulfuretted hydrogen starts to produce; Close the 15 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve keep action, peristaltic pump rotates forward, and pure water joins blow-off tube from the Chang Kaiduan of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 9: colorimetric pool absorbance A BSS is now read in analyser inside;
Step 10: air pump starts, 7th T-valve, the 8th T-valve are closed, 17 T-valve, the 18 T-valve valve open, air flow blasts from air pump and blasts bottom blow-off tube through T-shaped threeway, carry out stripping to the sulfide mixed liquor in blow-off tube, the hydrogen sulfide gas of blowout arrives absorbing liquid pipeline through the 18 T-valve and is absorbed; Air pump gassing time and the equal adjustable of tolerance, guarantee that sulfide stripping is complete, and stripping terminates rear all valves and air pump stops action;
Step 11: the 4th T-valve, the 17 T-valve valve event, peristaltic pump slow-speed, ferric chloride solution is quantitatively joined in suction line, now will absorbing liquid be allowed again to discharge, therefore the 17 T-valve is opened, even if the outlet that in mixing tube, liquid covers mixing tube upper side also can continue the rest using top, and upper gas is discharged from the 17 T-valve; Iron chloride quantitatively adds rear closedown the 4th T-valve, start the 5th T-valve, 17 T-valve keeps open, peristaltic pump slow-speed, N, N-dimethyl-p-phenylenediamine HCI solution is quantitatively joined in suction line, all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to the raw chromogenic reaction of abundant hybrid concurrency;
Step 12: leave standstill certain hour, treat that substance that show color absorbance reaches maximal value, after tending towards stability, instrument internal reads colorimetric pool absorbance A BSE now;
Step 13: instrument internal passes through ABSS and the ABSE value of known calibration value and sample, calculates the sulfide content of sample, in mg/L.
Further, also comprise measure data after step that stripping pipeline and suction line are cleaned; Cleaning step is: the method that the cleaning of suction line uses pure water to enter waste liquid to discharge, and can stop cleaning suction line when colorimetric pool absorbance is returned to pure water during absorbance; The cleaning of stripping pipeline will first be carried out emptying, and suction pure water afterwards, opens air pump aeration, is also cleaned up by the dirt of blow-off tube inwall, more emptying, stops whole analytic process after finally pumping into quantitative pure water again.
Adopt technique scheme, when in water sample of the present invention, dissolvable sulfide analyser is analyzed for the treatment of dissolvable sulfide in water sample, accurately can measure the dissolvable sulfide in water sample, particularly composition more complicated or itself with the water sample of colourity (as leather waste water, petrochemical wastewater etc.) in dissolvable sulfide also can be measured accurately, have can automatically detect, measuring accuracy advantages of higher.
Accompanying drawing explanation
Fig. 1 is dissolvable sulfide analyser structural representation of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
As shown in Figure 1, dissolvable sulfide analyser of the present invention, comprise the first T-valve 101, second T-valve 102, 3rd T-valve 103, 4th T-valve 104, 5th T-valve 105, 6th T-valve 106, 7th T-valve 107, 8th T-valve 108, 9th T-valve 109, tenth T-valve 110, 11 T-valve 111, 12 T-valve 112, 13 T-valve 113, 14 T-valve 114, 15 T-valve 115, 16 T-valve 116, 17 T-valve 117, air pump 122, peristaltic pump 123, mixing tube 118, colorimetric pool 119, blow-off tube 121, T-shaped threeway 120, be provided with an import bottom fixed tube 118, top and sidepiece are respectively provided with an outlet, be provided with a liquid-inlet bottom described blow-off tube 121, top is provided with a liquid outlet and a gas vent,
It should be noted that, in prior art, T-valve comprises normal-closed end, common port, Chang Kaiduan; When no power (when being failure to actuate), be common port and normal beginning intercommunication, normal-closed end and common port are then obstructed; When after energising, (when namely having action) is normal-closed end and the intercommunication of common port end, common port and normal beginning are then obstructed; In the application on the left of T-valve for normal-closed end, middle for common port, right side be Chang Kaiduan,
Concrete, first T-valve 101 normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, common port connects the normal-closed end of the second T-valve 102, and the second T-valve 102 Chang Kaiduan connects the 3rd T-valve 103 Chang Kaiduan, and common port connects the 4th T-valve 104 Chang Kaiduan; 3rd T-valve 103 normal-closed end connects waste solution channel, and common port connects colorimetric pool outlet; 4th T-valve 104 normal-closed end connects iron chloride pipeline, and common port connects the 5th T-valve 105 Chang Kaiduan; 5th T-valve 105 normal-closed end connects N, N-dimethyl-p-phenylenediamine hydrochloride pipeline, and common port connects the 6th T-valve 106 Chang Kaiduan; 6th T-valve 106 normal-closed end connects NaOH pipeline, and common port connects the 7th T-valve 107 Chang Kaiduan;
The 9th described T-valve 109 normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, common port connects the tenth T-valve 110 Chang Kaiduan; Tenth T-valve 110 normal-closed end connects sampling pipe, common port connects the 11 T-valve 111 Chang Kaiduan; 11 T-valve 111 normal-closed end connects mark liquid pipeline, common port connects the 12 T-valve 112 Chang Kaiduan; 12 T-valve 112 normal-closed end connects waste solution channel, and common port connects the 13 T-valve 113 Chang Kaiduan; 13 T-valve 113 Chang Kaiduan connects zinc sulfate pipeline, and common port connects the 14 T-valve 114 Chang Kaiduan; 14 T-valve 115 normal-closed end connects NaOH pipeline, and common port connects the 15 T-valve 115 Chang Kaiduan; 15 T-valve 116 normal-closed end connects sulfuric acid and hydrogen peroxide solution pipeline, and common port connects the 7th T-valve 107 normal-closed end;
The 7th described T-valve 107 common port connects peristaltic pump; 8th T-valve 108 normal-closed end connecting T-shaped threeway 120 first passage, common port connects peristaltic pump 123, Chang Kaiduan connects the 16 T-valve 116 Chang Kaiduan; 16 T-valve 116 normal-closed end connects blow-off tube 121 gas vent, and Chang Kaiduan connects mixing tube 118 import; Mixing tube 118 lateral outlet connects colorimetric pool 119 import, and top exit connects the 17 T-valve 117 normal-closed end; Described T-shaped threeway 120 second channel connects air pump 122, third channel connects blow-off tube 121 liquid-inlet; The 17 described T-valve 117 Chang Kaiduan connects blow-off tube 121 liquid outlet, and the pipeline that the 17 T-valve 117 connects blow-off tube 121 liquid outlet extends to the quantitative liquid level position place in blow-off tube 121, due to quantitative liquid, the 17 T-valve 117 common port connects waste solution channel;
The second described T-valve 102 and the 3rd T-valve 103 common action (i.e. energising simultaneously or simultaneously no power), the 7th T-valve 107 and the 8th T-valve 108 action simultaneously (i.e. energising simultaneously or simultaneously no power).
Concrete, the complete analysis process adopting dissolvable sulfide analyser of the present invention to carry out dissolvable sulfide analysis in water is:
Step 1: after instrument starts measurement, first the absorbing liquid carrying out sulfide suction line is taken into, first T-valve, second T-valve, 3rd T-valve (the second T-valve, 3rd T-valve is action simultaneously) valve event, peristaltic pump rotates forward, pure water is taken into the first T-valve from pure water pipeline, according to the opening and closing rule of valve, through the first T-valve after pure water enters from the first T-valve, second T-valve, 4th T-valve, 5th T-valve, 6th T-valve, 7th T-valve, 8th T-valve, enter from the lower end of mixing tube after 16 T-valve, liquid level flows out through colorimetric pool from this outlet after arriving the outlet of mixing tube upper lateral, final arrival the 3rd T-valve, discharge from the waste solution channel of the 3rd T-valve, then action is stopped after guaranteeing to be full of pure water in suction line,
Step 2: the 6th T-valve and the 3rd T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in suction line, and unnecessary liquid is drained from the waste solution channel overflow of the 3rd T-valve; The all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to abundant mixing;
Step 3: after completing the absorbing liquid preliminary work of suction line, 12 T-valve, 7th T-valve, 8th T-valve (the 7th T-valve, the action simultaneously of 8th T-valve, play switching effect, switching stream is to blow-off tube or to mixing tube) valve event, peristaltic pump reverses, the pure water stayed after cleaning in blow-off tube is carried out emptying: manage interior pure water through pipe lower end to T-shaped threeway, again through the 8th T-valve, 7th T-valve, 15 T-valve, 14 T-valve, 13 T-valve, 12 T-valve, discharge from the sewer pipe of the normal-closed end of the 12 T-valve, this process should ensure that the sewer pipe on the 17 T-valve above blow-off tube communicates with air, otherwise cannot complete emptying action, guarantee that blow-off tube is emptied completely by peristaltic pump reversion enough time,
Step 4: the tenth T-valve, the 7th T-valve, the 8th T-valve valve event, peristaltic pump rotates forward; Water sample is taken into from stopple coupon, according to the opening and closing rule of valve, after the tenth T-valve, the 11 T-valve, the 12 T-valve, the 13 T-valve, the 14 T-valve, the 15 T-valve, the 7th T-valve, the 8th T-valve, blow-off tube is arrived after water sample enters from stopple coupon, along with water sample amount increases, after water sample liquid level arrival the 7th T-valve Chang Kaiduan stretches into the surface of contact of the pipeline of blow-off tube, unnecessary water is just outwards drained from this pipeline, reaches quantitative sample injection amount 5.5cm height with this; Closedown the tenth T-valve after quantitative sample injection completes, the 7th, the 8th T-valve and peristaltic pump still keep action, and air enters from the 6th T-valve draft tube, is all pushed in blow-off tube by the water sample in pipeline, stops everything afterwards; The object entering air is to guarantee that water sample is quantitatively accurate, can not occur that water sample amount is inconsistent because of the length of sample introduction pipeline;
Step 5: the 14 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in blow-off tube from the normal-closed end of the 14 T-valve, 16 T-valve and the 17 T-valve action can ensure the circulation that can have air between blow-off tube and absorbing liquid, are unlikely to the loss having sulfide; Therefore complete to whole stripping process from this time, the 16 T-valve and the 17 T-valve all can keep operating state;
Step 6: close the 16 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump rotate forward, pure water from pure water pipeline join blow-off tube, quantitatively enter rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 7: the 13 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, solution of zinc sulfate is quantitatively joined in blow-off tube from the normal-closed end of the 13 T-valve, now can form White Flocculus; Close the 13 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve stay open simultaneously, peristaltic pump rotates forward, and pure water joins blow-off tube from the normal-closed end of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 8: the 15 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sulfuric acid and hydrogen peroxide solution (H
2sO
42N+20%H
2o
2) quantitatively joined in blow-off tube from the normal-closed end of the 15 T-valve, now White Flocculus disappears, and sulfuretted hydrogen starts to produce; Close the 15 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve keep action, peristaltic pump rotates forward, and pure water joins blow-off tube from the Chang Kaiduan of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 9: colorimetric pool absorbance A BSS is now read in analyser inside;
Step 10: air pump starts, 7th T-valve, the 8th T-valve are closed, 17 T-valve, the 18 T-valve valve open, air flow blasts from air pump and blasts bottom blow-off tube through T-shaped threeway, carry out stripping to the sulfide mixed liquor in blow-off tube, the hydrogen sulfide gas of blowout arrives absorbing liquid pipeline through the 18 T-valve and is absorbed; Air pump gassing time and the equal adjustable of tolerance, guarantee that sulfide stripping is complete, and stripping terminates rear all valves and air pump stops action;
Step 11: the 4th T-valve, the 17 T-valve valve event, peristaltic pump slow-speed, ferric chloride solution is quantitatively joined in suction line, now will absorbing liquid be allowed again to discharge, therefore the 17 T-valve is opened, even if the outlet that in mixing tube, liquid covers mixing tube upper side also can continue the rest using top, and upper gas is discharged from the 17 T-valve; Iron chloride quantitatively adds rear closedown the 4th T-valve, start the 5th T-valve, 17 T-valve keeps open, peristaltic pump slow-speed, N, N-dimethyl-p-phenylenediamine HCI solution is quantitatively joined in suction line, all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to the raw chromogenic reaction of abundant hybrid concurrency;
Step 12: leave standstill certain hour, treat that substance that show color absorbance reaches maximal value, after tending towards stability, instrument internal reads colorimetric pool absorbance A BSE now;
Step 13: instrument internal passes through ABSS and the ABSE value of known calibration value and sample, calculates the sulfide content of sample, in mg/L;
Step 14: will clean stripping pipeline and suction line after measuring data, the method that the cleaning of suction line uses pure water to enter waste liquid to discharge, can stop cleaning suction line during absorbance when colorimetric pool absorbance is returned to pure water; The cleaning of stripping pipeline will first be carried out emptying, and suction pure water afterwards, opens air pump aeration, is also cleaned up by the dirt of blow-off tube inwall, more emptying, stops whole analytic process after finally pumping into quantitative pure water again.
The blank correction of instrument and mark liquid trimming process keep consistance highly with water sample measuring process, just obstructed in sample introduction link, do blank correction and be then taken into pure water as sample from the 9th T-valve, do the correction of mark liquid and be then taken into titer as sample from the 11 T-valve, other the process such as emptying, stripping, reaction, cleaning is all the same, does not repeat at this.
Embodiment
When using the automatic analyzer of dissolvable sulfide in water of the present invention, mark liquid pipeline and sampling pipe are put into standard solution and sample respectively, analysis can be completed by automatic sampling, absorbance peak height according to the standard solution of record does typical curve, and absorbance peak height value per sample can calculate the content of dissolvable sulfide compounds in sample on typical curve.
Adopt automatic analyzer of the present invention to test, sample injection valve is T-valve, and the pump line specification of peristaltic pump is 3.2 × 6.4mm (internal diameter × external diameter), and the range of speeds of pump can from 10 revs/min to 300 revs/min.Mixing tube specification is 20 × 100mm (external diameter × length); Blow-off tube specification is 20 × 26 × 190mm (internal diameter × external diameter × length); Between mixing tube and blow-off tube, connecting pipe and drug-feeding tube specification are 1 × 1.5mm (internal diameter × external diameter); Sample feeding pipe, mark liquid pipe, sewer pipe and other connecting pipe specifications are 1.6 × 3.2mm (internal diameter × external diameter).The tolerance of air pump is 50 ml/min.The light path of flow cell is 50mm.The determined wavelength of detecting device is 660nm.
1, the preparation of standard specimen
Preparation of standard sample: take 1.9130g sodium sulphide (Na
2s9H
2o) be settled to 250ml, the sulfide storing solution being mixed with 1000mg/L is for subsequent use.
By the NaOH stepwise dilution of the sulfide storing solution 4g/L of 1000mg/L, be configured to 0.000,0.050,0.100,0.200,0.500,1.000,1.600,2.000mg/L titer series.
The medicament used in the present embodiment, iron chloride FeCl
36H
2the concentration of O is at 3g/L; N, N-dimethyl-p-phenylenediamine hydrochloride (C
6h
4nH
2n (CH
3) 22HCl) and concentration at 1g/L; The concentration of NaOH NaOH is at 40g/L; Sulfuric acid H
2sO
4concentration is 5.6% (volumn concentration); Hydrogen peroxide (H
2o
2) concentration is 20% (volumn concentration); Zinc sulfate (ZnSO
47H
2o) concentration is 56g/L.
When using the automatic analyzer of dissolvable sulfide in water of the present invention, mark liquid pipeline and sampling pipe are put into standard solution and sample respectively, analysis can be completed by automatic sampling, absorbance peak height according to the standard solution of record does typical curve, and absorbance peak height value per sample can calculate the content of dissolvable sulfide compounds in sample on typical curve.
Table 1 is the test result of standard model, and table 2 is the test result of actual sample, and table 3 is the Precision test result of actual sample medium sulphide content assay.
The test result of table 1 standard model
The test result (n=3) of table 2 actual sample
| Actual sample title | Sample concentration (mg/L) | Add scalar (mg/L) | Concentration (mg/L) after mark-on | The recovery |
| Surface water | 0.000 | 0.200 | 0.194 | 97.00％ |
| Underground water | 0.001 | 0.200 | 0.203 | 100.99％ |
| Draining outside Leather Factory | 0.496 | 0.200 | 0.684 | 98.28％ |
| The outer draining of petrochemical plant | 0.828 | 0.200 | 1.046 | 101.75％ |
| Petrochemical plant desulfurization wastewater | 1.795 | 0.200 | 2.048 | 102.66％ |
The Precision test result of table 3 actual sample medium sulphide content assay
The range of linearity of the inventive method is 0.02-2.0mg/L, and linearly dependent coefficient r >=0.999, detects and be limited to 0.001mg/L, and the recovery of standard addition of actual water sample is 90%-110%; Precision is high, and the sample relative standard deviation of 0.4mg/L is 0.728%.
Although specifically show in conjunction with preferred embodiment and describe the present invention; but those skilled in the art should be understood that; not departing from the spirit and scope of the present invention that appended claims limits; in the form and details the present invention is made a variety of changes, be protection scope of the present invention.
Claims (4)
1. a dissolvable sulfide analyser, is characterized in that: comprise the first to the 17 T-valve, air pump, peristaltic pump, mixing tube, colorimetric pool, blow-off tube, T-shaped threeway; Be provided with an import bottom described fixed tube, top and sidepiece are respectively provided with an outlet, are provided with a liquid-inlet bottom described blow-off tube, and top is provided with a liquid outlet and a gas vent;
The first described T-valve normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, and common port connects the normal-closed end of the second T-valve, and the second T-valve Chang Kaiduan connects the 3rd T-valve Chang Kaiduan, and common port connects the 4th T-valve Chang Kaiduan; 3rd T-valve normal-closed end connects waste solution channel, and common port connects colorimetric pool outlet; 4th T-valve normal-closed end connects iron chloride pipeline, and common port connects the 5th T-valve Chang Kaiduan; 5th T-valve normal-closed end connects N, N-dimethyl-p-phenylenediamine hydrochloride pipeline, and common port connects the 6th T-valve Chang Kaiduan; 6th T-valve normal-closed end connects NaOH pipeline, and common port connects the 7th T-valve Chang Kaiduan;
The 9th described T-valve normal-closed end connects pure water pipeline, Chang Kaiduan connects air duct, common port connects the tenth T-valve Chang Kaiduan; Tenth T-valve normal-closed end connects sampling pipe, common port connects the 11 T-valve Chang Kaiduan; 11 T-valve normal-closed end connects mark liquid pipeline, common port connects the 12 T-valve Chang Kaiduan; 12 T-valve normal-closed end connects waste solution channel, and common port connects the 13 T-valve Chang Kaiduan; 13 T-valve Chang Kaiduan connects zinc sulfate pipeline, and common port connects the 14 T-valve Chang Kaiduan; 14 T-valve normal-closed end connects NaOH pipeline, and common port connects the 15 T-valve Chang Kaiduan; 15 T-valve normal-closed end connects sulfuric acid and hydrogen peroxide solution pipeline, and common port connects the 7th T-valve normal-closed end;
The 7th described T-valve common port connects peristaltic pump; 8th T-valve normal-closed end connecting T-shaped threeway first passage, common port connects peristaltic pump, Chang Kaiduan connects the 16 T-valve Chang Kaiduan; 16 T-valve normal-closed end connects blow-off tube gas vent, and Chang Kaiduan connects mixing tube import; Mixing tube lateral outlet connects colorimetric pool import, and top exit connects the 17 T-valve normal-closed end; Described T-shaped threeway second channel connects air pump, third channel connects blow-off tube; The 17 described T-valve Chang Kaiduan connects blow-off tube liquid outlet, and the pipeline of the 17 T-valve connection blow-off tube liquid outlet extends to the quantitative liquid level position place in blow-off tube, and the 17 T-valve common port connects waste solution channel;
The second described T-valve and the 3rd T-valve common action, the 7th T-valve and the action simultaneously of the 8th T-valve.
2. a dissolvable sulfide analytical approach in water sample, is characterized in that in the water sample that claim 1 is above-mentioned, dissolvable sulfide analyser carries out dissolvable sulfide analysis in water sample.
3. dissolvable sulfide analytical approach according to claim 2, is characterized in that, comprise the steps:
Step 1: after instrument starts measurement, first the absorbing liquid carrying out sulfide suction line is taken into, first T-valve, second T-valve, 3rd T-valve action, wherein the second T-valve and the action simultaneously of the 3rd T-valve, peristaltic pump rotates forward, pure water is taken into the first T-valve from pure water pipeline, according to the opening and closing rule of valve, through the first T-valve after pure water enters from the first T-valve, second T-valve, 4th T-valve, 5th T-valve, 6th T-valve, 7th T-valve, 8th T-valve, enter from the lower end of mixing tube after 16 T-valve, liquid level flows out through colorimetric pool from this outlet after arriving the outlet of mixing tube upper lateral, final arrival the 3rd T-valve, discharge from the waste solution channel of the 3rd T-valve, then action is stopped after guaranteeing to be full of pure water in suction line,
Step 2: the 6th T-valve and the 3rd T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in suction line, and unnecessary liquid is drained from the waste solution channel overflow of the 3rd T-valve; The all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to abundant mixing;
Step 3: after completing the absorbing liquid preliminary work of suction line, the 12 T-valve, the 7th T-valve, the 8th T-valve action, wherein the 7th T-valve and the action simultaneously of the 8th T-valve, play the effect switching pipeline; Peristaltic pump reverses, the pure water stayed after cleaning in blow-off tube is carried out emptying: manage interior pure water through pipe lower end to T-shaped threeway, again through the 8th T-valve, the 7th T-valve, the 15 T-valve, the 14 T-valve, the 13 T-valve, the 12 T-valve, discharge from the sewer pipe of the normal-closed end of the 12 T-valve;
Step 4: the tenth T-valve, the 7th T-valve, the 8th T-valve action, peristaltic pump rotates forward; Water sample is taken into from stopple coupon, according to the opening and closing rule of valve, after the tenth T-valve, the 11 T-valve, the 12 T-valve, the 13 T-valve, the 14 T-valve, the 15 T-valve, the 7th T-valve, the 8th T-valve, blow-off tube is arrived after water sample enters from stopple coupon, along with water sample amount increases, after water sample liquid level arrival the 7th T-valve Chang Kaiduan stretches into the surface of contact of the pipeline of blow-off tube, unnecessary water is just outwards drained from this pipeline, reaches quantitative object with this; Closedown the tenth T-valve after quantitative sample injection completes, the 7th T-valve, the 8th T-valve and peristaltic pump still keep action, and air enters from the 6th T-valve draft tube, is all pushed in blow-off tube by the water sample in pipeline, stops everything afterwards;
Step 5: the 14 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sodium hydroxide solution is quantitatively joined in blow-off tube from the normal-closed end of the 14 T-valve;
Step 6: close the 16 T-valve, 9th T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump rotates forward, pure water from pure water pipeline join blow-off tube, quantitatively enter rear closedown the 9th T-valve, other valves and peristaltic pump keep action, and now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mix rear peristaltic pump and stop;
Step 7: the 13 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, solution of zinc sulfate is quantitatively joined in blow-off tube from the normal-closed end of the 13 T-valve, now forms White Flocculus; Close the 13 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve stay open simultaneously, peristaltic pump rotates forward, and pure water joins blow-off tube from the normal-closed end of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 8: the 15 T-valve, the 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve action, peristaltic pump slow-speed, sulfuric acid and hydrogen peroxide solution are quantitatively joined in blow-off tube from the normal-closed end of the 15 T-valve, now White Flocculus disappears, and sulfuretted hydrogen starts to produce; Close the 15 T-valve, open the 9th T-valve, 7th T-valve, the 8th T-valve, the 16 T-valve, the 17 T-valve keep action, peristaltic pump rotates forward, and pure water joins blow-off tube from the Chang Kaiduan of the 9th T-valve, quantitatively enters rear closedown the 9th T-valve, other valves and peristaltic pump keep action, now air enters from the Chang Kaiduan of the 9th T-valve, in order to mix the liquid in blow-off tube, mixes rear peristaltic pump and stops;
Step 9: colorimetric pool absorbance A BSS is now read in analyser inside;
Step 10: air pump starts, 7th T-valve, the 8th T-valve are closed, 17 T-valve, the 18 T-valve valve open, air flow blasts from air pump and blasts bottom blow-off tube through T-shaped threeway, carry out stripping to the sulfide mixed liquor in blow-off tube, the hydrogen sulfide gas of blowout arrives absorbing liquid pipeline through the 18 T-valve and is absorbed; Air pump gassing time and the equal adjustable of tolerance, guarantee that sulfide stripping is complete, and stripping terminates rear all valves and air pump stops action;
Step 11: the 4th T-valve, the 17 T-valve valve event, peristaltic pump slow-speed, ferric chloride solution is quantitatively joined in suction line, now will absorbing liquid be allowed again to discharge, therefore the 17 T-valve is opened, even if the outlet that in mixing tube, liquid covers mixing tube upper side also can continue the rest using top, and upper gas is discharged from the 17 T-valve; Iron chloride quantitatively adds rear closedown the 4th T-valve, start the 5th T-valve, 17 T-valve keeps open, peristaltic pump slow-speed, N, N-dimethyl-p-phenylenediamine HCI solution is quantitatively joined in suction line, all valves of closedown after dosing completes, peristaltic pump quick rotation makes suction line form home loop, and the liquid of the inside is able to the raw chromogenic reaction of abundant hybrid concurrency;
Step 12: leave standstill certain hour, treat that substance that show color absorbance reaches maximal value, after tending towards stability, instrument internal reads colorimetric pool absorbance A BSE now;
Step 13: instrument internal passes through ABSS and the ABSE value of known calibration value and sample, calculates the sulfide content of sample, in mg/L.
4. dissolvable sulfide analytical approach according to claim 3, is characterized in that, also comprises after measuring data the step that stripping pipeline and suction line clean; Cleaning step is: the method that the cleaning of suction line uses pure water to enter waste liquid to discharge, and can stop cleaning suction line when colorimetric pool absorbance is returned to pure water during absorbance; The cleaning of stripping pipeline will first be carried out emptying, and suction pure water afterwards, opens air pump aeration, is also cleaned up by the dirt of blow-off tube inwall, more emptying, stops whole analytic process after finally pumping into quantitative pure water again.
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| CN106198530A (en) * | 2016-08-29 | 2016-12-07 | 厦门市吉龙德环境工程有限公司 | Nutrient salt analyzer structure and the method for analysis thereof |
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| CN107367475B (en) * | 2017-07-20 | 2024-01-09 | 福建省吉龙德环保科技有限公司 | Water sample total cyanide analysis device and analysis method |
| CN110411988A (en) * | 2019-09-02 | 2019-11-05 | 中国热带农业科学院分析测试中心 | A kind of method of on-line continuous measurement Sulfide in Water |
| CN112378863A (en) * | 2020-09-30 | 2021-02-19 | 深圳市朗诚科技股份有限公司 | Water quality analysis method of water quality analyzer |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107290553B (en) | 2019-05-03 |
| CN107290553A (en) | 2017-10-24 |
| CN104977265B (en) | 2017-09-15 |
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