CN107515272B - Ammonia nitrogen on-line monitoring appearance based on distillation-titration method - Google Patents
Ammonia nitrogen on-line monitoring appearance based on distillation-titration method Download PDFInfo
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- CN107515272B CN107515272B CN201710759464.4A CN201710759464A CN107515272B CN 107515272 B CN107515272 B CN 107515272B CN 201710759464 A CN201710759464 A CN 201710759464A CN 107515272 B CN107515272 B CN 107515272B
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- 238000004448 titration Methods 0.000 title claims abstract description 117
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000012544 monitoring process Methods 0.000 title claims description 3
- 239000007788 liquid Substances 0.000 claims abstract description 302
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 248
- 238000010521 absorption reaction Methods 0.000 claims abstract description 90
- 238000005070 sampling Methods 0.000 claims abstract description 60
- 238000001514 detection method Methods 0.000 claims abstract description 38
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 238000005485 electric heating Methods 0.000 claims abstract description 11
- 239000007853 buffer solution Substances 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 92
- 239000004327 boric acid Substances 0.000 claims description 92
- 238000001704 evaporation Methods 0.000 claims description 73
- 230000008020 evaporation Effects 0.000 claims description 72
- 239000002699 waste material Substances 0.000 claims description 70
- 238000004140 cleaning Methods 0.000 claims description 63
- 239000000110 cooling liquid Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 25
- 239000000872 buffer Substances 0.000 claims description 24
- 238000002347 injection Methods 0.000 claims description 23
- 239000007924 injection Substances 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 7
- 238000011002 quantification Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000002352 surface water Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000088401 Pyrus pyrifolia Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012928 buffer substance Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
- G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
An ammonia nitrogen on-line monitor based on distillation-titration method comprises a sampling and pretreatment unit, a quantification unit, a distillation unit, an absorption titration unit, a post-treatment unit and a PLC controller. According to the invention, a liquid buffer solution is adopted to replace solid MgO, so that the automatic addition of a pH regulator is realized; the invention adopts the automatic distillation device with adjustable electric heating power and controllable distillation rate, improves the distillation efficiency and increases the safety and reliability of the instrument; the invention adopts a liquid automatic metering device with freely adjustable liquid amount to realize accurate quantification of water sample and absorption liquid; the invention adopts the pH potential detection electrode to automatically judge the titration end point, increases the sensitivity and accuracy of the instrument, and expands the measuring range of the instrument, so that the invention can be simultaneously suitable for the online automatic detection of surface water such as industrial sewage, domestic sewage, rivers, lakes and the like.
Description
Technical Field
The invention relates to an ammonia nitrogen on-line monitor, in particular to an ammonia nitrogen water quality on-line automatic monitor which is based on a distillation-neutralization titration method and is controlled by a PLC.
Background
The method for measuring ammonia nitrogen in water is more, and mainly comprises photometry, electrode method, distillation-titration method, gas phase molecular absorption spectrometry, ion chromatography, stripping-conductance method and the like according to different detection principles.
Currently, ammonia nitrogen online monitors which are relatively common in the market are mainly based on three methods, namely a photometry method, an electrode method and a distillation-titration method. The Nashi reagent and salicylic acid spectrophotometry are classical methods for measuring ammonia nitrogen in water, have the advantages of sensitivity, stability and the like, but are easily interfered by water impurities, colors, turbidity and suspended substances, the reagent is difficult to prepare, the stability requirement is strict, the operation is complex, and the accuracy of test data is poor. The continuous flow-salicylic acid spectrophotometry and the flow injection-salicylic acid spectrophotometry are both substantially salicylic acid spectrophotometry, have the same interference condition, and simultaneously have the problems of complex structure, limited measurement range, insufficient measurement precision and the like of a continuous flow analyzer and a flow injection analyzer. The common electrode in the electrode method is an ammonia gas sensitive electrode, the method generally does not need to pretreat a water sample, has wide measurement range, is not easy to interfere, is simple to operate and high in measurement speed, and is a preferred method for detecting ammonia nitrogen in water quality, but the ammonia gas sensitive electrode used in the method is extremely tender and easy to damage, has short service life, poor stability and reliability, low measurement precision and the like, and needs to be further solved.
The distillation-neutralization titration method is mainly suitable for measuring ammonia nitrogen in domestic sewage and industrial wastewater, has the characteristics of wide measurement range, no toxicity of reagents and waste liquid and the like, and is not influenced and interfered by chromaticity, turbidity and suspended substances in water. However, the method has the problems and technical difficulties that the stability time of the mixed indicator is short, the automatic addition of the solid magnesium oxide is difficult to realize, the automatic judgment of the titration end point (indicator color change point) is difficult to accurately realize, and the like.
Disclosure of Invention
The invention provides an ammonia nitrogen on-line monitor based on a distillation-titration method, which aims to solve the problems and technical difficulties that the stability time of a mixed indicator is short, the automatic addition of solid magnesium oxide is difficult to realize, the accurate automatic judgment of a titration end point is difficult to realize, and the like in the distillation-neutralization titration method. The problems of accurate sampling, solid MgO substitution, high-efficiency distillation, titration endpoint judgment, online automatic detection and the like in the online automatic detection of ammonia nitrogen by a distillation-neutralization titration method are solved, so that various technical performance indexes of an online ammonia nitrogen monitor are improved, and the accuracy, stability, reliability and adaptability of system measurement are improved; the titration detection electrode adopts the pH potential detection electrode, so that the sensitivity and the accuracy of the instrument are improved, the measurement range of the instrument is expanded, and the titration detection electrode not only can be suitable for detecting industrial sewage and domestic sewage, but also can be suitable for detecting surface water such as rivers, lakes and the like.
The technical scheme adopted for solving the technical problems is as follows:
an ammonia nitrogen on-line monitor based on a distillation-titration method comprises a sampling and pretreatment unit, a quantifying unit, a distillation unit, an absorption titration unit, a post-treatment unit and a PLC controller;
the sampling and pretreatment unit comprises a water sample pretreatment tank V1, wherein a tank body 2-1 of the water sample pretreatment tank V1 is in a hollow cylinder shape, and a sampling port 2-5, an acid adding port 2-3 and an alkali adding port 2-4, the outlets of which are communicated with the inner cavity of the water sample pretreatment tank V1, are sequentially arranged on a tank top 2-6 of the water sample pretreatment tank V1; the inlet of the acid adding port 2-3 is communicated with the acid tank V3 through an acid adding pump P3 and a matched pipeline, and the inlet of the alkali adding port 2-4 is communicated with the alkali tank V4 through an alkali adding pump P4 and a matched pipeline;
a first pH potential detection electrode J1, a first temperature sensor TE1 and a first stirrer MS1 are arranged in the water sample pretreatment tank V1; the top end of the first pH potential detection electrode J1, the top end of the first temperature sensor TE1 and the top end of the first stirrer MS1 are fixed on the tank top of the water sample pretreatment tank V1, and the bottom end of the first pH potential detection electrode J1, the bottom end of the first temperature sensor TE1 and the bottom end of the first stirrer MS1 extend into the water sample pretreatment tank V1;
The tank bottom 2-8 of the water sample pretreatment tank V1 is provided with a first liquid discharge pipe 2-9, an inlet of the first liquid discharge pipe 2-9 is communicated with an inner cavity of the water sample pretreatment tank V1, an outlet of the first liquid discharge pipe 2-9 is communicated with a discharge port PF, and the first liquid discharge pipe 2-9 is provided with a water sample pretreatment tank waste liquid valve S4;
two sides of the water sample pretreatment tank V1 are respectively provided with a water inlet pipe 2-2 and a first overflow pipe 2-7; the outlet of the water inlet pipe 2-2 is communicated with the inner cavity of the water sample pretreatment tank V1, the inlet of the water inlet pipe 2-2 is communicated with the first outlet of the water inlet pipeline a, the inlet of the water inlet pipeline a is communicated with the outlet of the sampling pump P1, the inlet of the sampling pump P1 is communicated with a water source, the second outlet of the water inlet pipeline a is communicated with the discharge outlet PF through a discharge pipe, and the discharge pipe is provided with a self-priming pump water outlet valve S2; a sample injection valve S3 of a water sample pretreatment tank is arranged on the water inlet pipe 2-2; the inlet of the first overflow pipe 2-7 is communicated with the inner cavity of the water sample pretreatment tank V1, the outlet of the first overflow pipe 2-7 is communicated with the discharge port PF, and the first overflow pipe 2-7 is provided with a water sample pretreatment tank overflow valve S5;
the quantitative unit comprises a water sample constant volume tank V2 and a boric acid constant volume tank V12, the tank body of the water sample constant volume tank V2 and the tank body of the boric acid constant volume tank V12 are cylindrical barrel bodies 3-3, and a top opening and a bottom opening of the barrel bodies 3-3 are respectively provided with a detachable top cover 3-1 and a detachable bottom cover 3-6; the bottom cover 3-6 is provided with a second liquid discharge pipe 3-8, the inlet of which is communicated with the inner cavity of the cylinder 3-3; the two sides of the cylinder body 3-3 are respectively provided with a first liquid inlet pipe 3-2 and a liquid outlet pipe 3-5, the first liquid inlet pipe 3-2 is positioned above the liquid outlet pipe 3-5, and the outlet of the first liquid inlet pipe 3-2 and the inlet of the liquid outlet pipe 3-5 are both communicated with the inner cavity of the cylinder body 3-3; the cylinder 3-3 is internally provided with a second overflow pipe 3-7 which can move up and down in a sealing way along the axial direction of the cylinder 3-3, the top end of the second overflow pipe 3-7 is positioned in the cylinder 3-3, the top opening of the second overflow pipe 3-7 is positioned above the liquid outlet pipe 3-5, and the bottom end of the second overflow pipe 3-7 penetrates through the bottom cover 3-6; the outer surface of the cylinder body 3-3 is provided with scales along the axial direction;
The outlet of the second liquid discharge pipe 3-8 of the water sample constant volume tank V2 is communicated with a discharge port PF, and a water sample constant volume tank waste liquid valve S6 is arranged on the second liquid discharge pipe 3-8 of the water sample constant volume tank V2; the inlet of the first liquid inlet pipe 3-2 of the water sample constant volume tank V2 is communicated with the outlet of the sampling port 2-5 of the water sample pretreatment tank V1 through a sampling pump P2 and a matched pipeline; the bottom end of the second overflow pipe 3-7 of the water sample constant volume tank V2 is communicated with the discharge port PF; a liquid outlet pipe 3-5 of the water sample constant volume tank V2 is provided with a water sample constant volume tank liquid discharge valve S8;
the outlet of the second liquid discharge pipe 3-8 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13, and the second liquid discharge pipe 3-8 of the boric acid constant volume tank V12 is provided with a boric acid constant volume tank waste liquid valve S14; the inlet of the first liquid inlet pipe 3-2 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13 through a boric acid pump P8 and a matched pipeline; a boric acid drain valve S13 is arranged on a drain pipe 3-5 of the boric acid constant volume tank V12; the bottom end of the second overflow pipe 3-7 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13;
the distillation unit comprises an evaporation tank V6, a condensation tank V8 and a jacketed straight tube cooler E1, wherein the condensation tank V8 is positioned above the evaporation tank V6, the inner cavity of the evaporation tank V6 is communicated with the inner cavity of the condensation tank V8 through a steam outlet pipe 4-4, and two ends of the steam outlet pipe 4-4 are respectively connected with a tank top 4-18 of the evaporation tank V6 and a tank bottom 4-10 of the condensation tank V8;
The tank body 4-17 of the evaporation tank V6 is in a hollow cylinder shape, and the tank top 4-18 of the evaporation tank V6 is respectively provided with a cleaning pipe 4-1, a second liquid inlet pipe 4-2 and a blow-down pipe 4-3;
the outlet of the cleaning pipe 4-1 is communicated with the inner cavity of the evaporation tank V6, the inlet of the cleaning pipe 4-1 is respectively communicated with the buffer liquid tank V5 and the cleaning liquid tank V7 through a buffer liquid pump P5 and a matched pipeline, the cleaning liquid pump P6 and a matched pipeline, and a buffer liquid valve S7 is arranged on the cleaning pipe 4-1;
the outlet of the second liquid inlet pipe 4-2 is communicated with the inner cavity of the evaporation tank V6, and the inlet of the second liquid inlet pipe 4-2 is communicated with the outlet of the liquid outlet pipe 3-5 of the water sample constant volume tank V2;
the inlet of the blow-down pipe 4-3 is communicated with the inner cavity of the evaporation tank V6, the outlet of the blow-down pipe 4-3 is communicated with the outside atmosphere, and an evaporation tank blow-down valve S9 is arranged on the blow-down pipe 4-3;
an electric heating disc H1 is arranged outside the tank bottom 4-16 of the evaporation tank V6, and the electric heating disc H1 is connected with a pressure regulating device capable of regulating heating power; the tank bottom 4-16 of the evaporation tank V6 is also provided with a third liquid discharge pipe 4-15, the top end of the third liquid discharge pipe 4-15 is communicated with the inner cavity of the evaporation tank V6, the bottom end of the third liquid discharge pipe 4-15 penetrates through the electric heating disc H1 in an insulating manner and is communicated with the waste liquid tank V9, and the third liquid discharge pipe 4-15 is also provided with an evaporation tank waste liquid valve S10;
The tank body 4-5 of the condensing tank V8 is hollow and cylindrical, the condensing tank jacket 4-8 is sleeved outside the tank body 4-5 of the condensing tank V8, a first cooling liquid outlet 4-7 and a first cooling liquid inlet 4-9 are respectively arranged on the upper side and the lower side of the condensing tank jacket 4-8, and the first cooling liquid outlet 4-7 and the first cooling liquid inlet 4-9 are respectively connected with a cooling system;
the jacket type straight pipe cooler E1 comprises a condensate liquid outlet pipe 4-14 and a cooling pipe jacket 4-12 sleeved outside the condensate liquid outlet pipe 4-14; the inlet of the condensate liquid outlet pipe 4-14 is communicated with the inner cavity of the condensation tank V8 at the tank bottom 4-10 of the condensation tank V8; the cooling pipe jacket 4-12 is respectively provided with a second cooling liquid outlet 4-11 and a second cooling liquid inlet 4-13, and the second cooling liquid outlet 4-11 and the second cooling liquid inlet 4-13 are respectively communicated with a cooling system;
the absorption titration unit comprises an absorption titration tank V10, wherein a tank body 5-8 of the absorption titration tank V10 is hollow and cylindrical, and a condensate pipe 5-3, an absorption liquid pipe 5-4 and a titration liquid pipe 5-5 are arranged on a tank top 5-2 of the absorption titration tank V10;
the outlet of the condensate pipe 5-3 is communicated with the inner cavity of the absorption titration tank V10, the inlet of the condensate pipe 5-3 is communicated with the outlet of the condensate liquid outlet pipe 4-14, and the condensate pipe 5-3 is provided with a condensate valve S12;
The outlet of the absorption liquid pipe 5-4 is communicated with the inner cavity of the absorption titration tank V10, and the inlet of the absorption liquid pipe 5-4 is communicated with the outlet of the liquid outlet pipe 3-5 of the boric acid constant volume tank V12;
a buret e is arranged in the buret 5-5, an inlet of the buret e is communicated with a buret tank V11 through a syringe pump P7 and a matched pipeline, and an outlet of the buret e is communicated with an inner cavity of an absorption buret tank V10;
the tank top 5-2 of the absorption titration tank V10 is also fixedly provided with a second pH potential detection electrode J2, a second temperature sensor TE2 and a liquid level electrode LS which extend into the absorption titration tank V10, and the tank bottom 5-6 of the absorption titration tank V10 is provided with a second stirrer MS2;
the side surface of the absorption titration tank V10 is respectively provided with a cleaning liquid pipe 5-1 and a fourth liquid discharge pipe 5-7; the outlet of the cleaning liquid pipe 5-1 is communicated with the inner cavity of the absorption titration tank V10, the inlet of the cleaning liquid pipe 5-1 is communicated with the cleaning liquid tank V7 through a cleaning liquid pump P6 and a matched pipeline, and the cleaning liquid pipe 5-1 is provided with a cleaning liquid valve S11;
the inlet of the fourth liquid discharge pipe 5-7 is communicated with the inner cavity of the absorption titration tank V10, the outlet of the fourth liquid discharge pipe 5-7 is communicated with the waste liquid tank V9, and the fourth liquid discharge pipe 5-7 is provided with an absorption titration tank waste liquid valve S15;
The self-priming pump outlet valve S2, the water sample pretreatment tank sample injection valve S3, the water sample pretreatment tank waste liquid valve S4, the water sample pretreatment tank overflow valve S5, the water sample constant volume tank waste liquid valve S6, the buffer liquid valve S7, the water sample constant volume tank drain valve S8, the evaporation tank drain valve S9, the evaporation tank waste liquid valve S10, the cleaning liquid valve S11, the condensate valve S12, the boric acid drain valve S13, the boric acid constant volume tank waste liquid valve S14 and the absorption titration tank waste liquid valve S15 are all electromagnetic valves, and the electromagnetic valves are respectively connected with the PLC;
the sampling pump P1, the sampling pump P2, the acid adding pump P3, the alkali adding pump P4, the buffer pump P5, the cleaning liquid pump P6, the injection pump P7, the boric acid pump P8, the first pH potential detection electrode J1, the first temperature sensor TE1, the first stirrer MS1, the second pH potential detection electrode J2, the second temperature sensor TE2, the liquid level electrode LS, the second stirrer MS2 and the pressure regulating device are respectively connected with the PLC.
Further, the second stirrer MS2 is a magnetic stirrer.
Further, a filter screen L is arranged at the inlet end of the sampling pump P1.
Further, the tank top 2-6 of the water sample pretreatment tank V1 is a plane, the tank bottom of the water sample pretreatment tank V1 is a conical end socket, and the first liquid discharge pipe 2-9 is arranged at the center of the conical end socket.
Further, the first stirrer MS1 is coaxially disposed with the water sample pretreatment tank V1.
Further, the top end of the second overflow pipe 3-7 is a flat opening.
Further, the top opening and the bottom opening of the cylinder body 3-3 are respectively in threaded connection with the top cover 3-1 and the bottom cover 3-6.
Further, the top 4-6 of the condensing tank is a butterfly-shaped end socket, and the bottom 4-10 of the condensing tank is a conical end socket.
Further, the first cooling liquid outlet 4-7 and the second cooling liquid outlet 4-11 are both communicated with the discharge port PF; the first cooling liquid inlet 4-9 and the second cooling liquid inlet 4-13 are communicated with the outlet end of the sampling pump P1 sequentially through a cooling water valve S1 and a third outlet of the water inlet pipeline a, the cooling water valve S1 is an electromagnetic valve, and the cooling water valve S1 is connected with the PLC.
Further, the matching structure of the cylinder 3-3 and the second overflow pipe 3-7 is as follows: the second overflow pipe 3-7 is connected with the cylinder 3-3 through a bolt, the bolt is positioned on the outer surface of the bottom cover 3-6, and the second overflow pipe 3-7 penetrates through the bolt and is meshed with the bolt.
In order to solve the unstable problems that the automatic addition of the light magnesia solid powder serving as a buffer substance is difficult, the adhered magnesia is difficult to clean, the solid magnesia is easy to denature and the like, the invention adopts a liquid buffer solution to replace the solid magnesia, thereby realizing the automatic metering and addition.
In order to solve the problems and technical difficulties that automatic determination of a titration end point is difficult to accurately realize, the invention adopts an electrochemical principle and a method, and adopts an automatic potentiometric titration technology to realize the determination of the titration end point so as to replace and solve the defects and shortcomings of an indicator determination end point in an automatic detection process in a new national standard method.
The beneficial effects of the invention are as follows: the ammonia nitrogen on-line automatic monitor solves the problems and technical difficulties that the mixed indicator in the existing distillation-neutralization titration method has short stabilizing time, solid magnesium oxide is difficult to realize automatic addition, titration endpoint is difficult to accurately realize automatic judgment, and the like. Liquid buffer solution is adopted to replace solid MgO, so that the automatic addition of the pH regulator is realized; an automatic distillation device with adjustable electric heating power and controllable distillation rate is adopted, so that the distillation efficiency is improved, and the safety and reliability of the instrument are improved; an automatic liquid metering device with freely adjustable liquid amount is adopted to realize accurate quantification of water samples and absorption liquid; the pH potential detection electrode is adopted to judge the titration end point, so that the sensitivity and the accuracy of the instrument are improved, the measurement range of the instrument is expanded, and the method can be simultaneously suitable for detecting surface water such as industrial sewage, domestic sewage, rivers, lakes and the like.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the present invention;
FIG. 2 is a schematic diagram of a water sample pretreatment tank according to the present invention;
FIG. 3 is a schematic diagram of the structure of the water sample constant volume tank of the invention;
FIG. 4 is a schematic diagram of the distillation unit structure of the present invention;
FIG. 5 is a schematic diagram of the structure of an absorption titration tank according to the present invention.
In FIG. 1, P1, sampling pump, P2, sampling pump, P3 . Acid pump, P4 . An alkali adding pump, a P5. buffer pump, a P6 cleaning liquid pump, a P7 injection pump, a P8 boric acid pump, a V1 water sample pretreatment tank (for containing a water sample to be tested), a V2 water sample constant volume tank (for containing a pretreated water sample to be tested), a V3. acid tank (for containing dilute sulfuric acid for adjusting the pH in the water sample pretreatment tank), a V4. alkali tank (for containing sodium hydroxide for adjusting the pH in the water sample pretreatment tank), a V5. buffer tank (for containing a mixed buffer for adjusting the pH in an evaporation tank), wherein the mixed buffer comprises Na 2 HPO 4 And NaOH in a ratio of 25:2), V6. evaporator (for holding a water sample of ammonia nitrogen to be distilled), V7. cleaning solution tank (for holding distilled water for cleaning), V8. condenser (for steam condensation), V9. waste solution tank (distilled waste solution and titrated waste solution tank), v10 absorption titration tank (absorption tank for absorbing ammonia gas after distillation), v11 titration tank (titrated hydrochloric acid solution tank) v12 boric acid constant volume tank (metering tank for absorption solution), v13 boric acid tank (absorption solution boric acid tank), e1 jacket type straight tube cooler, a water inlet pipeline, b water sample overflow pipe, c glass absorption tube, d boric acid overflow pipe, e buret, S1 cooling water valve, S2 self-priming pump water valve, S3 water sample pretreatment tank sample injection valve, S4 water sample pretreatment tank waste solution valve, S5 water sample pretreatment tank overflow valve, S6 constant volume tank waste solution valve, water sample valve, S7 water sample constant volume tank discharge valve, S8 water sample constant volume tank discharge valve, S9 evaporator tank discharge valve S10, S12 waste solution discharge valve S12 . Condensate valve, S13, boric acid drain valve, S14, boric acid constant volume tank waste liquid valve, S15, absorption titration tank waste liquid valve, MS1, first stirrer, MS2, second stirrer, TE1, first temperature sensor, TE2, second temperature sensor, J1, first pH potential detection electrode, J2, second pH potential detection electrode, L, filter screen, LS. liquid level electrode, the portion marked s in each solenoid valve in FIG. 1The component is the electrical control part, also called the driving part of the solenoid valve.
Description of the embodiments
An ammonia nitrogen on-line monitor based on a distillation-titration method comprises a sampling and pretreatment unit, a quantifying unit, a distillation unit, an absorption titration unit, a post-treatment unit and a PLC controller; and the PLC is internally provided with a control module and a data processing module.
The sampling and pretreatment unit comprises a water sample pretreatment tank V1, wherein a tank body 2-1 of the water sample pretreatment tank V1 is in a hollow cylinder shape, and a sampling port 2-5, an acid adding port 2-3 and an alkali adding port 2-4, the outlets of which are communicated with the inner cavity of the water sample pretreatment tank V1, are sequentially arranged on a tank top 2-6 of the water sample pretreatment tank V1; the inlet of the acid adding port 2-3 is communicated with the acid tank V3 through an acid adding pump P3 and a matched pipeline, and the inlet of the alkali adding port 2-4 is communicated with the alkali tank V4 through an alkali adding pump P4 and a matched pipeline;
A first pH potential detection electrode J1, a first temperature sensor TE1 and a first stirrer MS1 are arranged in the water sample pretreatment tank V1; the top end of the first pH potential detection electrode J1, the top end of the first temperature sensor TE1 and the top end of the first stirrer MS1 are fixed on the tank top of the water sample pretreatment tank V1, and the bottom end of the first pH potential detection electrode J1, the bottom end of the first temperature sensor TE1 and the bottom end of the first stirrer MS1 extend into the water sample pretreatment tank V1;
the tank bottom 2-8 of the water sample pretreatment tank V1 is provided with a first liquid discharge pipe 2-9, an inlet of the first liquid discharge pipe 2-9 is communicated with an inner cavity of the water sample pretreatment tank V1, an outlet of the first liquid discharge pipe 2-9 is communicated with a discharge port PF, and the first liquid discharge pipe 2-9 is provided with a water sample pretreatment tank waste liquid valve S4;
two sides of the water sample pretreatment tank V1 are respectively provided with a water inlet pipe 2-2 and a first overflow pipe 2-7; the outlet of the water inlet pipe 2-2 is communicated with the inner cavity of the water sample pretreatment tank V1, the inlet of the water inlet pipe 2-2 is communicated with the first outlet of the water inlet pipeline a, the inlet of the water inlet pipeline a is communicated with the outlet of the sampling pump P1, the inlet of the sampling pump P1 is communicated with a water source, the second outlet of the water inlet pipeline a is communicated with the discharge outlet PF through a discharge pipe, and the discharge pipe is provided with a self-priming pump water outlet valve S2; a sample injection valve S3 of a water sample pretreatment tank is arranged on the water inlet pipe 2-2; the inlet of the first overflow pipe 2-7 is communicated with the inner cavity of the water sample pretreatment tank V1, the outlet of the first overflow pipe 2-7 is communicated with the discharge port PF, and the first overflow pipe 2-7 is provided with a water sample pretreatment tank overflow valve S5;
The quantitative unit comprises a water sample constant volume tank V2 and a boric acid constant volume tank V12, the tank body of the water sample constant volume tank V2 and the tank body of the boric acid constant volume tank V12 are cylindrical barrel bodies 3-3, and a top opening and a bottom opening of the barrel bodies 3-3 are respectively provided with a detachable top cover 3-1 and a detachable bottom cover 3-6; the bottom cover 3-6 is provided with a second liquid discharge pipe 3-8, the inlet of which is communicated with the inner cavity of the cylinder 3-3; the two sides of the cylinder body 3-3 are respectively provided with a first liquid inlet pipe 3-2 and a liquid outlet pipe 3-5, the first liquid inlet pipe 3-2 is positioned above the liquid outlet pipe 3-5, and the outlet of the first liquid inlet pipe 3-2 and the inlet of the liquid outlet pipe 3-5 are both communicated with the inner cavity of the cylinder body 3-3; the cylinder 3-3 is internally provided with a second overflow pipe 3-7 which can move up and down in a sealing way along the axial direction of the cylinder 3-3, the top end of the second overflow pipe 3-7 is positioned in the cylinder 3-3, the top opening of the second overflow pipe 3-7 is positioned above the liquid outlet pipe 3-5, and the bottom end of the second overflow pipe 3-7 penetrates through the bottom cover 3-6; the outer surface of the cylinder body 3-3 is provided with scales along the axial direction;
the outlet of the second liquid discharge pipe 3-8 of the water sample constant volume tank V2 is communicated with a discharge port PF, and a water sample constant volume tank waste liquid valve S6 is arranged on the second liquid discharge pipe 3-8 of the water sample constant volume tank V2; the inlet of the first liquid inlet pipe 3-2 of the water sample constant volume tank V2 is communicated with the outlet of the sampling port 2-5 of the water sample pretreatment tank V1 through a sampling pump P2 and a matched pipeline; the bottom end of the second overflow pipe 3-7 of the water sample constant volume tank V2 is communicated with the discharge port PF; a liquid outlet pipe 3-5 of the water sample constant volume tank V2 is provided with a water sample constant volume tank liquid discharge valve S8;
The outlet of the second liquid discharge pipe 3-8 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13, and the second liquid discharge pipe 3-8 of the boric acid constant volume tank V12 is provided with a boric acid constant volume tank waste liquid valve S14; the inlet of the first liquid inlet pipe 3-2 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13 through a boric acid pump P8 and a matched pipeline; a boric acid drain valve S13 is arranged on a drain pipe 3-5 of the boric acid constant volume tank V12; the bottom end of the second overflow pipe 3-7 of the boric acid constant volume tank V12 is communicated with the boric acid tank V13;
the distillation unit comprises an evaporation tank V6, a condensation tank V8 and a jacketed straight tube cooler E1, wherein the condensation tank V8 is positioned above the evaporation tank V6, the inner cavity of the evaporation tank V6 is communicated with the inner cavity of the condensation tank V8 through a steam outlet pipe 4-4, and two ends of the steam outlet pipe 4-4 are respectively connected with a tank top 4-18 of the evaporation tank V6 and a tank bottom 4-10 of the condensation tank V8;
the tank body 4-17 of the evaporation tank V6 is in a hollow cylinder shape, and the tank top 4-18 of the evaporation tank V6 is respectively provided with a cleaning pipe 4-1, a second liquid inlet pipe 4-2 and a blow-down pipe 4-3;
the outlet of the cleaning pipe 4-1 is communicated with the inner cavity of the evaporation tank V6, the inlet of the cleaning pipe 4-1 is respectively communicated with the buffer liquid tank V5 and the cleaning liquid tank V7 through a buffer liquid pump P5 and a matched pipeline, the cleaning liquid pump P6 and a matched pipeline, and a buffer liquid valve S7 is arranged on the cleaning pipe 4-1;
The outlet of the second liquid inlet pipe 4-2 is communicated with the inner cavity of the evaporation tank V6, and the inlet of the second liquid inlet pipe 4-2 is communicated with the outlet of the liquid outlet pipe 3-5 of the water sample constant volume tank V2;
the inlet of the blow-down pipe 4-3 is communicated with the inner cavity of the evaporation tank V6, the outlet of the blow-down pipe 4-3 is communicated with the outside atmosphere, and an evaporation tank blow-down valve S9 is arranged on the blow-down pipe 4-3;
an electric heating disc H1 is arranged outside the tank bottom 4-16 of the evaporation tank V6, and the electric heating disc H1 is connected with a pressure regulating device capable of regulating heating power; the tank bottom 4-16 of the evaporation tank V6 is also provided with a third liquid discharge pipe 4-15, the top end of the third liquid discharge pipe 4-15 is communicated with the inner cavity of the evaporation tank V6, the bottom end of the third liquid discharge pipe 4-15 penetrates through the electric heating disc H1 in an insulating manner and is communicated with the waste liquid tank V9, and the third liquid discharge pipe 4-15 is also provided with an evaporation tank waste liquid valve S10;
the tank body 4-5 of the condensing tank V8 is hollow and cylindrical, the condensing tank jacket 4-8 is sleeved outside the tank body 4-5 of the condensing tank V8, a first cooling liquid outlet 4-7 and a first cooling liquid inlet 4-9 are respectively arranged on the upper side and the lower side of the condensing tank jacket 4-8, and the first cooling liquid outlet 4-7 and the first cooling liquid inlet 4-9 are respectively connected with a cooling system;
the jacket type straight pipe cooler E1 comprises a condensate liquid outlet pipe 4-14 and a cooling pipe jacket 4-12 sleeved outside the condensate liquid outlet pipe 4-14; the inlet of the condensate liquid outlet pipe 4-14 is communicated with the inner cavity of the condensation tank V8 at the tank bottom 4-10 of the condensation tank V8; the cooling pipe jacket 4-12 is respectively provided with a second cooling liquid outlet 4-11 and a second cooling liquid inlet 4-13, and the second cooling liquid outlet 4-11 and the second cooling liquid inlet 4-13 are respectively communicated with a cooling system;
The absorption titration unit comprises an absorption titration tank V10, wherein a tank body 5-8 of the absorption titration tank V10 is hollow and cylindrical, and a condensate pipe 5-3, an absorption liquid pipe 5-4 and a titration liquid pipe 5-5 are arranged on a tank top 5-2 of the absorption titration tank V10;
the outlet of the condensate pipe 5-3 is communicated with the inner cavity of the absorption titration tank V10, the inlet of the condensate pipe 5-3 is communicated with the outlet of the condensate liquid outlet pipe 4-14, and the condensate pipe 5-3 is provided with a condensate valve S12;
the outlet of the absorption liquid pipe 5-4 is communicated with the inner cavity of the absorption titration tank V10, and the inlet of the absorption liquid pipe 5-4 is communicated with the outlet of the liquid outlet pipe 3-5 of the boric acid constant volume tank V12;
a buret e is arranged in the buret 5-5, an inlet of the buret e is communicated with a buret tank V11 through a syringe pump P7 and a matched pipeline, and an outlet of the buret e is communicated with an inner cavity of an absorption buret tank V10;
the tank top 5-2 of the absorption titration tank V10 is also fixedly provided with a second pH potential detection electrode J2, a second temperature sensor TE2 and a liquid level electrode LS which extend into the absorption titration tank V10, and the tank bottom 5-6 of the absorption titration tank V10 is provided with a second stirrer MS2;
the side surface of the absorption titration tank V10 is respectively provided with a cleaning liquid pipe 5-1 and a fourth liquid discharge pipe 5-7; the outlet of the cleaning liquid pipe 5-1 is communicated with the inner cavity of the absorption titration tank V10, the inlet of the cleaning liquid pipe 5-1 is communicated with the cleaning liquid tank V7 through a cleaning liquid pump P6 and a matched pipeline, and the cleaning liquid pipe 5-1 is provided with a cleaning liquid valve S11;
The inlet of the fourth liquid discharge pipe 5-7 is communicated with the inner cavity of the absorption titration tank V10, the outlet of the fourth liquid discharge pipe 5-7 is communicated with the waste liquid tank V9, and the fourth liquid discharge pipe 5-7 is provided with an absorption titration tank waste liquid valve S15;
the self-priming pump outlet valve S2, the water sample pretreatment tank sample injection valve S3, the water sample pretreatment tank waste liquid valve S4, the water sample pretreatment tank overflow valve S5, the water sample constant volume tank waste liquid valve S6, the buffer liquid valve S7, the water sample constant volume tank drain valve S8, the evaporation tank drain valve S9, the evaporation tank waste liquid valve S10, the cleaning liquid valve S11, the condensate valve S12, the boric acid drain valve S13, the boric acid constant volume tank waste liquid valve S14 and the absorption titration tank waste liquid valve S15 are all electromagnetic valves, and the electromagnetic valves are respectively connected with the PLC;
the sampling pump P1, the sampling pump P2, the acid adding pump P3, the alkali adding pump P4, the buffer pump P5, the cleaning liquid pump P6, the injection pump P7, the boric acid pump P8, the first pH potential detection electrode J1, the first temperature sensor TE1, the first stirrer MS1, the second pH potential detection electrode J2, the second temperature sensor TE2, the liquid level electrode LS, the second stirrer MS2 and the pressure regulating device are respectively connected with the PLC.
The second stirrer MS2 is a magnetic stirrer.
The inlet end of the sampling pump P1 is provided with a filter screen L.
The tank top 2-6 of the water sample pretreatment tank V1 is a plane, the tank bottom of the water sample pretreatment tank V1 is a conical end socket, and the first liquid discharge pipe 2-9 is arranged at the center of the conical end socket.
The first stirrer MS1 is coaxially arranged with the water sample pretreatment tank V1.
The top end of the second overflow pipe 3-7 is a flat opening.
The top opening and the bottom opening of the cylinder body 3-3 are respectively in threaded connection with the top cover 3-1 and the bottom cover 3-6.
The top 4-6 of the condensing tank is a butterfly-shaped sealing head, and the bottom 4-10 of the condensing tank is a conical sealing head.
The first cooling liquid outlet 4-7 and the second cooling liquid outlet 4-11 are both communicated with the discharge port PF; the first cooling liquid inlet 4-9 and the second cooling liquid inlet 4-13 are communicated with the outlet end of the sampling pump P1 sequentially through a cooling water valve S1 and a third outlet of the water inlet pipeline a, the cooling water valve S1 is an electromagnetic valve, and the cooling water valve S1 is connected with the PLC.
The matching structure of the cylinder 3-3 and the second overflow pipe 3-7 is as follows: the second overflow pipe 3-7 is connected with the cylinder 3-3 through a bolt, the bolt is positioned on the outer surface of the bottom cover 3-6, and the second overflow pipe 3-7 penetrates through the bolt and is meshed with the bolt.
The injection pump P7 is an industrial injection pump; the first temperature sensor TE1 and the second temperature sensor TE2 are Pt100 armored thermal resistors; the injection pump P7 is an industrial injection pump, the sampling pump P1 is a self-priming pump, the sampling pump P2, the acid adding pump P3, the alkali adding pump P4, the buffer pump P5, the cleaning pump P6 and the boric acid injection pump P8 are peristaltic pumps, and the first pH potential detection electrode J1 and the second pH potential detection electrode J2 are composite pH potential detection electrodes; the liquid level switch LS is an electrode type liquid level switch.
The ammonia nitrogen on-line automatic monitor of the invention as shown in fig. 1-5 comprises a sampling and preprocessing unit, a quantifying unit, a distilling unit, an absorption titration unit, a post-processing unit and a PLC control and data processing unit (namely a PLC controller).
The sampling and pretreatment unit consists of a water sample pretreatment tank V1, a sampling pump P1, an acid adding pump P3, an alkali adding pump P4 and the like. As shown in fig. 2, the water sample pretreatment tank V1 is a hollow cylindrical tank body 2-1, the inner top surface 2-6 of the tank is a plane, and the tank top 2-6 is provided with a pH potential detection electrode J1, a temperature sensor TE1 and a first stirrer MS1; the tank top 2-6 is additionally provided with a sampling port 2-5, an acid adding port 2-3 and an alkali adding port 2-4; the side surface of the tank is provided with a water inlet pipe 2-2 and an overflow pipe 2-7; the tank bottom 2-8 is a conical end socket, and a first liquid discharge pipe 2-9 is arranged in the center of the conical end socket. Further, a sample injection valve S3 of the water sample pretreatment tank, an overflow valve S5 of the water sample pretreatment tank and a waste liquid valve S4 of the water sample pretreatment tank are respectively arranged on the water inlet pipe 2-2, the overflow pipe 2-7 and the first liquid discharge pipe 2-9, and the electromagnetic valves are connected with the PLC; a filter screen L is arranged in front of the sampling pump P1, and a water inlet pipeline a of the sampling pump P1 is respectively connected with a cooling water valve S1, a self-priming pump water outlet valve S2 and a sample injection valve S3 of the water sample pretreatment tank; the acid adding pump P3 is respectively connected with an acid adding port 2-3 of the water sample pretreatment tank and an acid tank V3 through a silica gel pipe; and the alkali adding pump P4 is respectively connected with an alkali adding port 2-4 of the water sample pretreatment tank and the alkali tank V4 through a silica gel pipe.
The sampling and preprocessing unit is started, and the self-priming pump outlet valve S2 is opened 、 The water sample pretreatment tank sampling valve S3 and the water sample pretreatment tank overflow valve S5 are started, the sampling pump P1 is started, a water sample is sucked into the sampling pump P1 through the filter screen L, flows into the water sample pretreatment tank V1 through the water inlet pipeline a, overflows through the overflow pipe 2-7 after being full of liquid, overflows to the discharge port PF, overflows for a period of time, and the sampling pump P1, the water sample pretreatment tank overflow valve S5 and the water sample pretreatment tank sampling valve S3 are closed to finish water sample collection. Meanwhile, the first stirrer MS1 is turned on, the pH of the water sample is detected through the pH electrode J1, and when the pH of the water sample is detected to be too large, the acid adding pump P3 is turned on to adjust the pH of the water sample to be neutral, and then the acid adding pump P3 is turned off; when the pH of the water sample is too small, the alkali pump P4 is turned on to adjust the pH of the water sample to be neutral, and then the alkali adding pump P4 is turned off. Meanwhile, the temperature sensor TE1 transmits a real-time temperature signal to the PLC.
The quantitative unit comprises a water sample constant volume tank V2, a sampling pump P2, a boric acid constant volume tank V12, a boric acid pump P8 and the like. As shown in fig. 3, the water sample constant volume tank V2 and the boric acid constant volume tank V12 are hollow cylindrical barrels 3-3, a top cover 3-1 and a bottom cover 3-6 with threads are respectively arranged at the top and the bottom of the barrels 3-3, scale marks are arranged on the surfaces of the barrels 3-3, a first liquid inlet pipe 3-2 and a liquid outlet pipe 3-5 are respectively arranged on the upper part and the lower part of the side surface, and a second liquid outlet pipe 3-8 is arranged on the bottom cover; the cylinder body 3-3 is internally provided with a second overflow pipe 3-7, the second overflow pipe 3-7 vertically penetrates through the bottom cover 3-6 in the axial direction, one end of the second overflow pipe extends to the inner cavity of the cylinder body 3-3, and the other end of the second overflow pipe extends out of the cylinder body 3-3; the upper and lower positions of the second overflow pipe 3-7 are adjustable, the upper end of the second overflow pipe 3-7 is provided with a flush overflow port, and the height of the upper end is higher than the upper edge of the liquid outlet pipe 3-5; the liquid outlet pipe 3-5 and the second liquid outlet pipe 3-8 are respectively provided with a water sample constant volume tank waste liquid valve S6, a water sample constant volume tank drain valve S8, a boric acid constant volume tank waste liquid valve S14 and a boric acid drain valve S13, and the electric valves are connected with a PLC; the sampling pump P2 is respectively connected with a first liquid inlet pipe 3-2 of the water sample constant volume tank and a sampling port 2-5 of the water sample pretreatment tank through a silica gel pipe; the boric acid pump P8 is respectively connected with the first liquid inlet pipe 3-2 of the boric acid constant volume tank and the boric acid tank V13 through silica gel pipes.
When the water sample collection and pretreatment are finished, the PLC control and data processing unit controls the boric acid pump P8 to work, meanwhile, the boric acid discharging valve S13 and the boric acid constant volume tank waste liquid valve S14 are closed, boric acid in the boric acid tank V13 is conveyed into the boric acid constant volume tank V12, the liquid level in the boric acid constant volume tank V12 rises until overflow, and overflowed boric acid flows back to the boric acid tank V13 through the overflow pipeline d (connected with the second overflow pipe 3-7 of the boric acid constant volume tank V12). After overflowing for a certain time, the boric acid pump P8 is closed, then the boric acid pump is kept stand for a certain time, the boric acid drain valve S13 is opened, and after the quantitative boric acid in the boric acid constant volume tank V12 completely flows into the absorption titration tank V10, the boric acid drain valve S13 is closed. The absorption titration tank V10 is completely closed in feeding, the PLC controller controls the sampling pump P2 to work, meanwhile, the water sample constant volume tank liquid discharge valve S8 and the water sample constant volume tank waste liquid valve S6 are closed, the water sample in the water sample pretreatment tank V1 is conveyed to the water sample constant volume tank V2, the liquid level in the water sample constant volume tank V2 rises until overflow, and overflowed water sample is discharged into the discharge port PF through the overflow pipeline b (connected with the second overflow pipe 3-7 of the water sample constant volume tank V2). After overflowing for a certain time, the sampling pump P2 is closed, after standing still for a certain time, the water sample constant volume tank liquid discharge valve S8 is opened, and after the quantitative water sample in the water sample constant volume tank V2 completely flows into the evaporation tank V6, the water sample constant volume tank liquid discharge valve S8 is closed.
When the water sample is fed, the PLC control and data processing unit controls the starting of the buffer pump P5 and the opening of the buffer valve S7, and the buffer valve S7 is closed after the quantitative dripping of the buffer solution makes the water sample in the evaporation tank V6 alkalescent, and meanwhile, the buffer pump P5 is closed.
The distillation unit comprises an evaporation tank V6, a condensation tank V8 and a jacketed straight-tube cooler E1. As shown in fig. 4, the tank body 4-17 of the evaporation tank V6 is cylindrical, and the tank top 4-18 and the tank bottom 4-16 are both plane surfaces; the top 4-18 of the evaporation tank V6 is provided with a cleaning pipe 4-1, a second liquid inlet pipe 4-2, a blow-down pipe 4-3 and a steam outlet pipe 4-4, and the bottom 4-16 is provided with a third liquid outlet pipe 4-15. The cleaning pipe 4-1, the second liquid inlet pipe 4-2, the blow-down pipe 4-3 and the third liquid outlet pipe 4-15 are respectively provided with a buffer solution valve S7, a water sample constant volume tank blow-down valve S8, an evaporation tank blow-down valve S9 and an evaporation tank waste liquid valve S10, and the electromagnetic valves are all connected with the PLC; the outer bottom surface of evaporation jar V6 is provided with electrical heating dish H1, electrical heating dish H1 is connected with adjustable heating power's pressure regulating device, and pressure regulating device links to each other with the PLC controller. The condensing tank V8 is a cylindrical tank body 4-5 provided with a condensing tank jacket (4-8), and a cooling liquid outlet 4-7 and a cooling liquid inlet 4-9 are respectively arranged on the upper side surface and the lower side surface of the condensing tank jacket (4-8) and are connected with a cooling system; the top 4-6 of the condensing tank is a butterfly-shaped sealing head, the bottom 4-10 of the condensing tank is a conical sealing head, and the condensate liquid outlet pipe 4-14 is positioned at the center of the conical sealing head. The jacket 4-12 is provided with a cooling liquid outlet 4-11 and a cooling liquid inlet 4-13 which are connected with a cooling system.
After the water sample and the buffer solution are quantitatively added into the evaporation tank V6 in sequence, the PLC control and data processing unit controls the sampling pump P1 to be started, the cooling water valve S1 and the magnetic force second stirrer MS2 are opened, meanwhile, the pressure regulating device is controlled to heat and distill the evaporation tank V6, ammonia in the water sample rapidly escapes along with the rising of the water temperature, the water sample is condensed in the condensation tank V8 along with the water vapor after being boiled, and the water sample enters the absorption titration tank V10 through the glass absorption tube c after being further cooled in the jacket type straight tube cooler E1, and is absorbed by boric acid solution quantitatively added in advance. After distillation for a certain time (liquid level electrode LS is conducted), the PLC controls the pressure regulating device to stop heating, and a certain amount of distillate is obtained.
The absorption titration unit mainly comprises an absorption titration tank V10, a second stirrer MS2, a syringe pump P7 and the like. The tank body 5-8 of the absorption titration tank V10 is cylindrical, and the tank top 5-2 and the tank bottom 5-6 are both planes; the top 5-2 of the absorption titration tank V10 is provided with a condensate pipe 5-3, an absorption liquid pipe 5-4 and a titration liquid pipe 5-5, the condensate pipe 5-3 and the absorption liquid pipe 5-4 are respectively provided with a condensate valve S12 and a boric acid liquid discharge valve S13, and the electromagnetic valves are connected with a PLC; the tank top 5-2 is provided with a second pH electrode J2, a second temperature sensor TE2 and a liquid level electrode LS, and is inserted into the center of the tank; the pH electrode J2 is a composite potential detection electrode, the second temperature sensor TE2 is a Pt100 armored thermal resistor, and the liquid level electrode LS is a bipolar liquid level electrode; the side surface of the tank is provided with a cleaning liquid pipe 5-1 and a fourth liquid discharge pipe 5-7, the cleaning liquid pipe 5-1 and the fourth liquid discharge pipe 5-7 are respectively provided with a cleaning liquid valve S11 and an absorption titration tank waste liquid valve S15, and the electromagnetic valves are connected with a PLC; the second stirrer MS2 is a magnetic stirrer and is arranged at the bottom of the absorption titration tank V10; the injection pump P7 is an industrial injection pump and is respectively connected with the burette 5-5 of the absorption titration tank V10 and the titration liquid tank V11 through the burette e.
When the liquid level electrode LS is conducted, the PLC control and data processing unit closes the condensate valve S12, the injection pump P7 is started, the titration liquid is injected into the absorption titration tank V10 through the titration tank e to perform neutralization titration, and the second pH potential detection electrode J2 and the second temperature sensor TE2 respectively input pH potential signals and temperature signals detected in the titration process into the PLC control and data processing unit continuously. Meanwhile, the PLC control and data processing unit judges the titration end point according to the temperature signal and the pH potential signal of the titration liquid, stops the injection pump P7, calculates the actual content of ammonia nitrogen in the water sample according to the titration amount of the injection pump P7, and stores and displays the actual content.
The post-treatment unit comprises two parts of waste liquid discharge and cleaning. After each titration analysis is completed, residual liquid in the water sample pretreatment tank V1, the water sample constant volume tank V2, the boric acid constant volume tank V12, the evaporation tank V6 and the absorption titration tank V10 is completely discharged and is cleaned for the next online sampling analysis. The waste liquid of the water sample pretreatment tank V1 and the water sample constant volume tank V2 is directly discharged to the discharge port PF, the boric acid in the boric acid constant volume tank V12 is discharged to the boric acid tank V13, and the waste liquid of the evaporation tank V6 and the absorption titration tank V10 is discharged to the waste liquid tank V9. The water sample pretreatment tank V1 and the water sample constant volume tank V2 are pre-washed by water to be detected, and the evaporation tank V6 and the absorption titration tank V10 are both washed by distilled water, and the distilled water is conveyed by a washing liquid pump P6. The water sample pretreatment tank V1, the water sample constant volume tank V2, the boric acid constant volume tank V12, the evaporation tank V6 and the absorption titration tank V10 are respectively provided with a water sample pretreatment tank waste liquid valve S4, a water sample constant volume tank waste liquid valve S6, a boric acid constant volume tank waste liquid valve S14, an evaporation tank waste liquid valve S10 and an absorption titration tank waste liquid valve S15 on liquid discharge pipes, and the electromagnetic valves are all connected with the PLC.
The post-treatment of the water sample constant volume tank V2 is as follows: opening a water sample constant volume tank waste liquid valve S6, and closing the water sample constant volume tank waste liquid valve S6 after the bottom of the water sample constant volume tank V2 discharges liquid for a certain time; starting a sampling pump P2, closing the sampling pump P2 and opening a water sample constant volume tank waste liquid valve S6 when the water sample in the water sample constant volume tank is ensured to be full of the water sample to the upper overflow port after the sample is injected for a certain period of time; after the bottom of the water sample constant volume tank discharges liquid for a certain time, the water sample constant volume tank waste liquid valve S6 is closed. The post-treatment of the water sample pretreatment tank V1 is the same as the water sample constant volume tank V2, and is not repeated here.
Post-treatment step of the evaporation tank V6: when the temperature in the evaporation tank V6 is reduced to below 50 ℃, a water sample constant volume tank drain valve S8, an evaporation tank drain valve S9 and an evaporation tank waste liquid valve S10 are opened, and after liquid is drained for a certain time, the valve water sample constant volume tank drain valve S8 and the evaporation tank waste liquid valve S10 are closed. After the residual liquid is drained, opening a buffer valve S7, and starting a cleaning liquid pump P6; after a proper amount of distilled water is extracted from the cleaning solution tank V7, the buffer solution valve S7 and the cleaning solution pump P6 are closed; after standing and cleaning for a certain time, opening a waste liquid valve S10 of the evaporating pot; after a certain period of time, the evaporator waste liquid valve S10 and the evaporator emptying valve S9 are closed.
The steps of draining the residual liquid and cleaning the titration tank V10 are similar to those of the evaporation tank V6 and are not repeated here. After the completion of the cleaning of the absorption titration tank V10, a certain amount of distilled water is extracted from the cleaning liquid tank V7 for immersing and protecting the pH electrode J2.
The ammonia nitrogen on-line monitor automatically controls the working processes of other units through the PLC control and data processing unit, calculates, displays, prints and stores detection values to exchange information through the data communication port, and can conveniently form a network.
The working flow of the ammonia nitrogen on-line automatic monitor of the invention is as follows: starting, water sample collection, water sample pretreatment, boric acid quantification and adding an absorption titration tank, water sample quantification and adding an evaporation tank, buffer solution quantification and adding an evaporation tank, heating distillation, absorption, finishing distillation, neutralization titration, titration end point judgment, measurement value calculation, display, printing, measurement value storage, waste liquid discharge, cleaning and waiting for starting the next detection.
The embodiments described in the present specification are merely examples of implementation forms of the inventive concept, and the scope of protection of the present invention should not be construed as being limited to the specific forms set forth in the embodiments, but also equivalent technical means that can be conceived by those skilled in the art according to the inventive concept.
Claims (9)
1. An ammonia nitrogen on-line monitoring appearance based on distillation-titration method, its characterized in that: the device comprises a sampling and preprocessing unit, a quantifying unit, a distilling unit, an absorption titration unit, a post-processing unit and a PLC controller;
the sampling and pretreatment unit comprises a water sample pretreatment tank (V1), wherein a tank body (2-1) of the water sample pretreatment tank (V1) is in a hollow cylinder shape, and a sampling port (2-5), an acid adding port (2-3) and an alkali adding port (2-4) which are communicated with the inner cavity of the water sample pretreatment tank (V1) are sequentially arranged on a tank top (2-6) of the water sample pretreatment tank (V1); the inlet of the acid adding port (2-3) is communicated with the acid tank (V3) through an acid adding pump (P3) and a matched pipeline, and the inlet of the alkali adding port (2-4) is communicated with the alkali tank (V4) through an alkali adding pump (P4) and a matched pipeline;
a first pH potential detection electrode (J1), a first temperature sensor (TE 1) and a first stirrer (MS 1) are arranged in the water sample pretreatment tank (V1); the top end of the first pH potential detection electrode (J1), the top end of the first temperature sensor (TE 1) and the top end of the first stirrer (MS 1) are fixed on the tank top of the water sample pretreatment tank (V1), and the bottom end of the first pH potential detection electrode (J1), the bottom end of the first temperature sensor (TE 1) and the bottom end of the first stirrer (MS 1) extend into the water sample pretreatment tank (V1);
The water sample pretreatment tank is characterized in that a first liquid discharge pipe (2-9) is arranged on the tank bottom (2-8) of the water sample pretreatment tank (V1), an inlet of the first liquid discharge pipe (2-9) is communicated with an inner cavity of the water sample pretreatment tank (V1), an outlet of the first liquid discharge pipe (2-9) is communicated with a discharge Port (PF), and a water sample pretreatment tank waste liquid valve (S4) is arranged on the first liquid discharge pipe (2-9);
two sides of the water sample pretreatment tank (V1) are respectively provided with a water inlet pipe (2-2) and a first overflow pipe (2-7); the outlet of the water inlet pipe (2-2) is communicated with the inner cavity of the water sample pretreatment tank (V1), the inlet of the water inlet pipe (2-2) is communicated with the first outlet of the water inlet pipeline (a), the inlet of the water inlet pipeline (a) is communicated with the outlet of the sampling pump (P1), the inlet of the sampling pump (P1) is communicated with a water source, the second outlet of the water inlet pipeline (a) is communicated with the discharge Port (PF) through a discharge pipe, and the discharge pipe is provided with a self-priming pump water outlet valve (S2); a sample injection valve (S3) of the water sample pretreatment tank is arranged on the water inlet pipe (2-2); the inlet of the first overflow pipe (2-7) is communicated with the inner cavity of the water sample pretreatment tank (V1), the outlet of the first overflow pipe (2-7) is communicated with the discharge Port (PF), and the overflow valve (S5) of the water sample pretreatment tank is arranged on the first overflow pipe (2-7);
The quantitative unit comprises a water sample constant volume tank (V2) and a boric acid constant volume tank (V12), the tank body of the water sample constant volume tank (V2) and the tank body of the boric acid constant volume tank (V12) are cylindrical barrels (3-3), and a top opening and a bottom opening of the barrels (3-3) are respectively provided with a detachable top cover (3-1) and a detachable bottom cover (3-6); the bottom cover (3-6) is provided with a second liquid discharge pipe (3-8) with an inlet communicated with the inner cavity of the cylinder body (3-3); the two sides of the cylinder body (3-3) are respectively provided with a first liquid inlet pipe (3-2) and a liquid outlet pipe (3-5), the first liquid inlet pipe (3-2) is positioned above the liquid outlet pipe (3-5), and the outlet of the first liquid inlet pipe (3-2) and the inlet of the liquid outlet pipe (3-5) are both communicated with the inner cavity of the cylinder body (3-3); a second overflow pipe (3-7) capable of moving up and down along the axial direction of the cylinder (3-3) is arranged in the cylinder (3-3), the top end of the second overflow pipe (3-7) is positioned in the cylinder (3-3), the top opening of the second overflow pipe (3-7) is positioned above the liquid outlet pipe (3-5), and the bottom end of the second overflow pipe (3-7) penetrates through the bottom cover (3-6); the outer surface of the cylinder body (3-3) is provided with scales along the axial direction;
the outlet of the second liquid discharge pipe (3-8) of the water sample constant volume tank (V2) is communicated with a discharge Port (PF), and a water sample constant volume tank waste liquid valve (S6) is arranged on the second liquid discharge pipe (3-8) of the water sample constant volume tank (V2); an inlet of a first liquid inlet pipe (3-2) of the water sample constant volume tank (V2) is communicated with an outlet of a sampling port (2-5) of the water sample pretreatment tank (V1) through a sampling pump (P2) and a matched pipeline; the bottom end of a second overflow pipe (3-7) of the water sample constant volume tank (V2) is communicated with a discharge Port (PF); a liquid outlet pipe (3-5) of the water sample constant volume tank (V2) is provided with a water sample constant volume tank liquid discharge valve (S8);
The outlet of the second liquid discharge pipe (3-8) of the boric acid constant volume tank (V12) is communicated with the boric acid tank (V13), and a boric acid constant volume tank waste liquid valve (S14) is arranged on the second liquid discharge pipe (3-8) of the boric acid constant volume tank (V12); the inlet of the first liquid inlet pipe (3-2) of the boric acid constant volume tank (V12) is communicated with the boric acid tank (V13) through a boric acid pump (P8) and a matched pipeline; a boric acid drain valve (S13) is arranged on a drain pipe (3-5) of the boric acid constant volume tank (V12); the bottom end of a second overflow pipe (3-7) of the boric acid constant volume tank (V12) is communicated with the boric acid tank (V13);
the distillation unit comprises an evaporation tank (V6), a condensation tank (V8) and a jacketed straight pipe cooler (E1), wherein the condensation tank (V8) is positioned above the evaporation tank (V6), the inner cavity of the evaporation tank (V6) is communicated with the inner cavity of the condensation tank (V8) through a steam outlet pipe (4-4), and two ends of the steam outlet pipe (4-4) are respectively connected with the tank top (4-18) of the evaporation tank (V6) and the tank bottom (4-10) of the condensation tank (V8);
the tank body (4-17) of the evaporation tank (V6) is hollow and cylindrical, and the tank top (4-18) of the evaporation tank (V6) is respectively provided with a cleaning pipe (4-1), a second liquid inlet pipe (4-2) and a blow-down pipe (4-3);
The outlet of the cleaning pipe (4-1) is communicated with the inner cavity of the evaporation tank (V6), the inlet of the cleaning pipe (4-1) is respectively communicated with the buffer liquid tank (V5) and the cleaning liquid tank (V7) through the buffer liquid pump (P5) and the matched pipeline, the cleaning liquid pump (P6) and the matched pipeline, and the cleaning pipe (4-1) is provided with a buffer liquid valve (S7);
the outlet of the second liquid inlet pipe (4-2) is communicated with the inner cavity of the evaporation tank (V6), and the inlet of the second liquid inlet pipe (4-2) is communicated with the outlet of the liquid outlet pipe (3-5) of the water sample constant volume tank (V2);
the inlet of the blow-down pipe (4-3) is communicated with the inner cavity of the evaporation tank (V6), the outlet of the blow-down pipe (4-3) is communicated with the outside atmosphere, and an evaporation tank blow-down valve (S9) is arranged on the blow-down pipe (4-3);
an electric heating disc (H1) is arranged outside the tank bottom (4-16) of the evaporation tank (V6), and the electric heating disc (H1) is connected with a pressure regulating device capable of regulating heating power; the tank bottom (4-16) of the evaporation tank (V6) is also provided with a third liquid discharge pipe (4-15), the top end of the third liquid discharge pipe (4-15) is communicated with the inner cavity of the evaporation tank (V6), the bottom end of the third liquid discharge pipe (4-15) penetrates through the electric heating disc (H1) in an insulating way and is communicated with the waste liquid tank (V9), and the third liquid discharge pipe (4-15) is also provided with an evaporation tank waste liquid valve (S10);
The tank body (4-5) of the condensing tank (V8) is hollow and cylindrical, the condensing tank jacket (4-8) is sleeved outside the tank body (4-5) of the condensing tank (V8), a first cooling liquid outlet (4-7) and a first cooling liquid inlet (4-9) are respectively arranged on the upper side and the lower side of the condensing tank jacket (4-8), and the first cooling liquid outlet (4-7) and the first cooling liquid inlet (4-9) are respectively connected with a cooling system;
the jacket type straight pipe cooler (E1) comprises a condensate liquid outlet pipe (4-14) and a cooling pipe jacket (4-12) sleeved outside the condensate liquid outlet pipe (4-14); an inlet of the condensate liquid outlet pipe (4-14) is communicated with an inner cavity of the condensing tank (V8) at the tank bottom (4-10) of the condensing tank (V8); the cooling pipe jacket (4-12) is respectively provided with a second cooling liquid outlet (4-11) and a second cooling liquid inlet (4-13), and the second cooling liquid outlet (4-11) and the second cooling liquid inlet (4-13) are respectively communicated with a cooling system;
the absorption titration unit comprises an absorption titration tank (V10), a tank body (5-8) of the absorption titration tank (V10) is in a hollow cylinder shape, and a condensate pipe (5-3), an absorption liquid pipe (5-4) and a titration liquid pipe (5-5) are arranged on a tank top (5-2) of the absorption titration tank (V10);
The outlet of the condensate pipe (5-3) is communicated with the inner cavity of the absorption titration tank (V10), the inlet of the condensate pipe (5-3) is communicated with the outlet of the condensate liquid outlet pipe (4-14), and a condensate valve (S12) is arranged on the condensate pipe (5-3);
the outlet of the absorption liquid pipe (5-4) is communicated with the inner cavity of the absorption titration tank (V10), and the inlet of the absorption liquid pipe (5-4) is communicated with the outlet of the liquid outlet pipe (3-5) of the boric acid constant volume tank (V12);
a buret (e) is arranged in the buret (5-5), an inlet of the buret (e) is communicated with a buret tank (V11) through a syringe pump (P7) and a matched pipeline, and an outlet of the buret e is communicated with an inner cavity of an absorption buret tank (V10);
the tank top (5-2) of the absorption titration tank (V10) is also fixedly provided with a second pH potential detection electrode (J2), a second temperature sensor (TE 2) and a liquid level electrode (LS) which extend into the absorption titration tank (V10), and the tank bottom (5-6) of the absorption titration tank (V10) is provided with a second stirrer (MS 2);
the side surface of the absorption titration tank (V10) is respectively provided with a cleaning liquid pipe (5-1) and a fourth liquid discharge pipe (5-7); the outlet of the cleaning liquid pipe (5-1) is communicated with the inner cavity of the absorption titration tank (V10), the inlet of the cleaning liquid pipe (5-1) is communicated with the cleaning liquid tank (V7) through a cleaning liquid pump (P6) and a matched pipeline, and a cleaning liquid valve (S11) is arranged on the cleaning liquid pipe (5-1);
An inlet of the fourth liquid discharge pipe (5-7) is communicated with an inner cavity of the absorption titration tank (V10), an outlet of the fourth liquid discharge pipe (5-7) is communicated with the waste liquid tank (V9), and an absorption titration tank waste liquid valve (S15) is arranged on the fourth liquid discharge pipe (5-7);
the self-priming pump water outlet valve (S2), the water sample pretreatment tank sample injection valve (S3), the water sample pretreatment tank waste liquid valve (S4), the water sample pretreatment tank overflow valve (S5), the water sample constant volume tank waste liquid valve (S6), the buffer solution valve (S7), the water sample constant volume tank drain valve (S8), the evaporation tank drain valve (S9), the evaporation tank waste liquid valve (S10), the cleaning liquid valve (S11), the condensate valve (S12), the boric acid drain valve (S13), the boric acid constant volume tank waste liquid valve (S14) and the absorption titration tank waste liquid valve (S15) are all electromagnetic valves, and the electromagnetic valves are respectively connected with the PLC;
the sampling pump (P1), the sampling pump (P2), the acid adding pump (P3), the alkali adding pump (P4), the buffer liquid pump (P5), the cleaning liquid pump (P6), the injection pump (P7), the boric acid pump (P8), the first pH potential detection electrode (J1), the first temperature sensor (TE 1), the first stirrer (MS 1), the second pH potential detection electrode (J2), the second temperature sensor (TE 2), the liquid level electrode (LS), the second stirrer (MS 2) and the pressure regulating device are respectively connected with the PLC;
The tank top (2-6) of the water sample pretreatment tank (V1) is a plane, the tank bottom of the water sample pretreatment tank (V1) is a conical end socket, and the first liquid discharge pipe (2-9) is arranged at the center of the conical end socket.
2. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 1, wherein: the second stirrer (MS 2) is a magnetic stirrer.
3. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 2, wherein: the inlet end of the sampling pump (P1) is provided with a filter screen (L).
4. An ammonia nitrogen on-line monitor based on distillation-titration method as claimed in claim 3, wherein: the first stirrer (MS 1) and the water sample pretreatment tank (V1) are coaxially arranged.
5. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 4, wherein: the top end of the second overflow pipe (3-7) is a flat opening.
6. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 5, wherein: the top opening and the bottom opening of the cylinder body (3-3) are respectively in threaded connection with the top cover (3-1) and the bottom cover (3-6).
7. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 6, wherein: the top (4-6) of the condensing tank is a butterfly-shaped end socket, and the bottom (4-10) of the condensing tank is a conical end socket.
8. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 7, wherein: the first cooling liquid outlet (4-7) and the second cooling liquid outlet (4-11) are both communicated with the discharge port PF; the first cooling liquid inlet (4-9) and the second cooling liquid inlet (4-13) are communicated with the outlet end of the sampling pump (P1) sequentially through a cooling water valve (S1) and a third outlet of the water inlet pipeline (a), the cooling water valve (S1) is an electromagnetic valve, and the cooling water valve (S1) is connected with the PLC.
9. The ammonia nitrogen on-line monitor based on distillation-titration method as set forth in claim 8, wherein: the matching structure of the cylinder body (3-3) and the second overflow pipe (3-7) is as follows: the second overflow pipe (3-7) is connected with the cylinder (3-3) through a bolt, the bolt is positioned on the outer surface of the bottom cover (3-6), and the second overflow pipe (3-7) penetrates through the bolt and is meshed with the bolt.
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| CN108364888A (en) * | 2018-02-11 | 2018-08-03 | 武汉华星光电半导体显示技术有限公司 | Detection device |
| CN108982597A (en) * | 2018-10-10 | 2018-12-11 | 浙江工业大学 | It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method |
| CN110441469A (en) * | 2019-09-19 | 2019-11-12 | 威海长青海洋科技股份有限公司 | A kind of water body ammonia nitrogen detection kit and detection method |
| DE102019134611A1 (en) * | 2019-12-16 | 2021-06-17 | Endress+Hauser Conducta Gmbh+Co. Kg | Titration apparatus and titration process |
| CN112082983A (en) * | 2020-09-08 | 2020-12-15 | 浙江工业大学 | Machine vision-based water body hexavalent chromium detection method |
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