CN108982597A - It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method - Google Patents

It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method Download PDF

Info

Publication number
CN108982597A
CN108982597A CN201811177631.5A CN201811177631A CN108982597A CN 108982597 A CN108982597 A CN 108982597A CN 201811177631 A CN201811177631 A CN 201811177631A CN 108982597 A CN108982597 A CN 108982597A
Authority
CN
China
Prior art keywords
tank
outlet
pipe
water sample
valve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811177631.5A
Other languages
Chinese (zh)
Inventor
孙小方
钟毅
童谦
蔡亦军
潘海天
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201811177631.5A priority Critical patent/CN108982597A/en
Publication of CN108982597A publication Critical patent/CN108982597A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G01N27/07—Construction of measuring vessels; Electrodes therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/42—Low-temperature sample treatment, e.g. cryofixation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat

Abstract

The invention discloses a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method, and automonitor includes water sampling and pretreatment unit, sampling unit, distillation unit, absorption detecting unit, post-processing unit and PLC control unit.The present invention reduces interference of the Complex water body to measurement using distillation pretreatment；The problems such as present invention substitutes neutralization titration using conductance method, and elimination titration end-point is difficult to accurately determine automatically and the titrimetry time is long；The present invention uses a kind of automatic liquid metering device of twoport side overflow, realizes the accurate measurement of water sample and absorbing liquid；The present invention uses electrode constant to measure absorbing liquid conductivity for 0.1 platinum black electrode, improve the sensitivity and accuracy of instrument, the measurement range for extending instrument enables the invention to the on-line monitoring for adapting to the surface water various concentration occasions such as industrial wastewater, sanitary sewage, tap water, rivers and lakes.

Description

It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method
Technical field
The present invention relates to ammonia nitrogen water quality online auto monitoring engineering device technique fields, and in particular to one kind is based on distillation-conductance The ammonia nitrogen water quality online automatic monitor and method of method.
Background technique
The analysis method of ammonia nitrogen is more, according to the difference of testing principle, the measuring method of ammonia nitrogen can be divided into spectrophotometric Method, electrode method, distillation-neutralization titration, Blow-off-conductometry, the chromatography of ions, gas-phase molecular absorption spectrometry method, enzyme process and glimmering Light method etc..Currently, common ammonia nitrogen water quality online automatic monitor is based primarily upon spectrophotometry, electrode method and steaming in the market Evaporate-neutralization titration this three classes method.
Spectrophotometry is that domestic ammonia nitrogen analysis uses most common method, and nessler reagent and salicylic acid spectrophotometry are The classical way for measuring ammonia nitrogen in water has many advantages, such as sensitive, stabilization, but vulnerable to water body impurity, color, turbidity and suspended material Interference, reagent it is more difficult preparation and stability requirement it is stringent, operate it is more complicated, test data accuracy is poor.Continuous flowing- Salicylic acid spectrophotometry and flow injection-salicylic acid spectrophotometry are substantially salicylic acid spectrophotometry, disturbed condition It is identical, at the same structure is complicated, measurement range is limited there is also Continuous Flow Analysis instrument and flow injection analyzer, measurement accuracy not The problems such as enough high.
Common electrode is ammonia gas-sensing electrode in electrode method, is a kind of ion selective electrode, which measures ammonia nitrogen concentration It does not need to pre-process water sample, disturbing factor is few, measurement range is wide, is a kind of easy to operate, quick detection side of measurement Method, but ammonia gas-sensing electrode used in the method is extremely delicate, is easily damaged, service life is shorter, stability and reliability it is poor, The problems such as measurement accuracy is not high need to further solve.
Distillation-neutralization titration is primarily adapted for use in the measurement of sanitary sewage and ammonia nitrogen in industrial waste water, has measurement range Wide, the features such as reagent and waste liquid are non-toxic, meanwhile, after water sample is by distillation pretreatment, measurement result not vulnerable to the coloration of water body, Turbidity, suspended material etc. influence and interference.But there are the mixed indicator stable time, short, solid pH adjusting agent is difficult to realize the method Automatically addition, titration end-point (indicator discoloration point) are difficult to the problems such as being accurately realized automatic judgement and longer titrimetry time With technological difficulties.
Summary of the invention
Stablize that the time is short, solid pH adjusting agent is difficult to solve mixed indicator present in distillation-neutralization titration Realize that addition automatically, titration end-point are difficult to accurately realize the problems such as automatic judgement and titrimetry time are longer and technological difficulties, The present invention provides a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method, solves distillation-neutralization drop Determine in the ammonia nitrogen water quality online automatic detection of method accurately sampling, solid pH adjusting agent substitution, speed change distillation, online automatic detection etc. Problem, and replace neutralization titration to eliminate titration end-point come the content of ammonia nitrogen in accurate, quick measurement water sample by conductance method The problems such as being difficult to accurate automatic judgement and long titrimetry time, to improve every technology of ammonia nitrogen water quality online automatic monitor Performance indicator, and improve accuracy, stability, reliability and the adaptability of apparatus measures；And the present invention use electrode constant for 0.1 platinum black electrode improves the sensitivity and accuracy of instrument, extends the measurement range of instrument, adapt to it not only The monitoring water quality on line of the low concentrations occasion such as tap water, rivers and lakes, while also adapting to the waste water of industry and city discharge, life The monitoring water quality on line of the higher concentrations occasions such as sewage living.
The technical solution adopted by the present invention to solve the technical problems is:
It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, including water sampling and pretreatment unit, Sampling unit, distillation unit, absorption detecting unit, post-processing unit and PLC control unit；
The water sampling and pretreatment unit includes water sample pretreatment tank V1, the tank body of the water sample pretreatment tank V1 2-1 is in hollow cylindrical shape, and is successively arranged outlet on the tank deck 2-6 of water sample pretreatment tank V1 and pre-processes tank V1 with water sample Inner cavity the sample tap 2-5, plus the alkali mouth 2-4 and acid-adding port 2-3 that are connected；And the import of the acid-adding port 2-3 is pumped by acid adding P3 and be connected to acid tank V3 with circuits, described plus alkali mouth 2-4 import is by adding alkali pump P4 and matching circuits and alkali tank V4 company It is logical；
PH potentiometric detection electrode J1, temperature sensor TE1 and the first blender are equipped in the water sample pretreatment tank V1 MS1；The top on the top of the pH potentiometric detection electrode J1, the top of temperature sensor TE1 and the first blender MS1 is fixed On the tank deck of water sample pretreatment tank V1, and the bottom end of the pH potentiometric detection electrode J1, the bottom end of temperature sensor TE1 and the The bottom end of one blender MS1 all extends in water sample pretreatment tank V1；
The tank bottom 2-8 of water sample pretreatment tank V1 is equipped with the first drain pipe 2-9, the import of the first drain pipe 2-9 with The inner cavity of water sample pretreatment tank V1 is connected, and the outlet of the first drain pipe 2-9 is connected to discharge outlet PF, and the first drain pipe 2-9 It is equipped with water sample and pre-processes tank waist valve S4；
The two sides of the water sample pretreatment tank V1 are respectively equipped with water inlet pipe 2-2 and the first overflow pipe 2-7；Water inlet pipe 2-2's It exporting and is connected with the inner cavity of water sample pretreatment tank V1, the import of water inlet pipe 2-2 is connected to the first outlet of water inlet pipeline a, The import of the water inlet pipeline a is connected with the outlet of sampling pump P1, and the import of the sampling pump P1 is connected with water source, and The second outlet of the water inlet pipeline a is connected to by delivery pipe with discharge outlet PF, and the delivery pipe is discharged equipped with self priming pump Valve S2；The water inlet pipe 2-2 is equipped with water sample and pre-processes tank sampling valve S3；The import of the first overflow pipe 2-7 and water sample are pre- The inner cavity of process tank V1 is connected to, and the outlet of the first overflow pipe 2-7 is connected to discharge outlet PF, and the first overflow pipe 2-7 is equipped with water Sample pre-processes tank overflow valve S5；
The sampling unit includes water sample constant volume overflow tank V2 and boric acid constant volume overflow tank V11, and water sample constant volume overflow The tank body of tank V2 and the tank body of boric acid constant volume overflow tank V11 are cylindrical tube 3-2, and the top opening of the cylinder 3-2 and bottom Mouth is respectively provided with dismountable top cover 3-7 and bottom cover 3-3；Second drain pipe 3-4 of the inner cavity cylinder 3-2 connection；Cylinder 3-2 Two sides be respectively equipped with the first inlet tube 3-1 and outlet tube 3-5, the first inlet tube 3-1 are located at the top of outlet tube 3-5, and The outlet of one inlet tube 3-1 and the import of outlet tube 3-5 are connected to the inner cavity of cylinder 3-2；Second overflow pipe 3-6 and cylinder 3- The connection of 2 inner cavities, and the import of the second overflow pipe 3-6 is located on outlet tube 3-5；
The outlet of the second drain pipe 3-4 of the water sample constant volume overflow tank V2 is connected with discharge outlet PF, and water sample constant volume The second drain pipe 3-4 of overflow tank V2 is equipped with water sample constant volume overflow tank waist valve S6；The of the water sample constant volume overflow tank V2 The import of one inlet tube 3-1 pre-processes the outlet of the sample tap 2-5 of tank V1 by sampling pump P2 and with circuits and the water sample Connection；The outlet of the second overflow pipe 3-6 of the water sample constant volume overflow tank V2 is connected to discharge outlet PF；The water sample constant volume overflow The outlet tube 3-5 of tank V2 is equipped with water sample constant volume overflow tank bleeder valve S8；
The outlet of the second drain pipe 3-4 of the boric acid constant volume overflow tank V11 is connected with boric acid tank V12, and boric acid is fixed The the second drain pipe 3-4 for holding overflow tank V11 is equipped with boric acid constant volume overflow tank waist valve S14；The boric acid constant volume overflow tank V11 The import of the first inlet tube 3-1 P7 is pumped by boric acid and is connected to circuits with boric acid tank V12；The boric acid constant volume overflow tank The outlet tube 3-5 of V11 is equipped with boric acid bleeder valve S13；The outlet of the second overflow pipe 3-6 of the boric acid constant volume overflow tank V11 It is connected with boric acid tank V12；
The distillation unit includes evaporator V6, drainer V8 and jacket type straight tube cooler E1, the drainer V8 Positioned at the top of the evaporator V6, and the inner cavity of the evaporator V6 and the inner cavity of the drainer V8 pass through steam outlet pipe 4-4 It is connected, and steam outlet pipe 4-4 has certain length, prevents liquid bumping from buffer solution being caused to damage with the entrainment of steam It loses, and the both ends of steam outlet pipe 4-4 are connected with the tank bottom 4-9 of the tank deck 4-16 of evaporator V6 and drainer V8 respectively, and coolant liquid The both ends of communicating pipe G1 are connected with drainer V8 with jacket type straight tube cooler E1 respectively, and cooling liquid outlet 4-7 and coolant liquid Import 4-12 is connect with cooling system respectively；
The tank body 4-15 of the evaporator V6 is in hollow cylindrical shape, and the tank deck 4-16 of evaporator V6 is respectively equipped with clearly Wash pipe 4-1, the second inlet tube 4-2 and blow-down pipe 4-3；
The outlet of the cleaning pipe 4-1 is connected to the inner cavity of evaporator V6, and the import of the cleaning pipe 4-1 passes through slow respectively Fliud flushing pumps P5 and is connected with circuits, cleaning liquid pump P6 and with circuits with buffering flow container V5, cleaning fluid tank V7, and described clear Pipe 4-1 is washed equipped with buffer valve S7；
The outlet of the second inlet tube 4-2 is connected to the inner cavity of evaporator V6, the import of the second inlet tube 4-2 and water sample The outlet of the outlet tube 3-5 of constant volume overflow tank V2 is connected；
The import of the blow-down pipe 4-3 is connected to the inner cavity of evaporator V6, the outlet and ambient atmosphere of the blow-down pipe 4-3 It is connected, and blow-down pipe 4-3 is equipped with evaporator blow valve S9；
The tank bottom 4-14 of the evaporator V6 is externally provided with electric heating plate H1, and the electric heating plate H1 is connected with adjustable heating The regulator of power；The tank bottom 4-14 of evaporator V6 is additionally provided with third drain pipe 4-13, the top of third drain pipe 4-13 with The inner cavity of evaporator V6 is connected, and the bottom end insulation of third drain pipe 4-13 is connected through electric heating plate H1 and with waste liquid tank V9 It is logical, and evaporator waist valve S10 is additionally provided on third drain pipe 4-13；
The tank body 4-5 of the drainer V8 is in hollow cylindrical shape, and is arranged with outside the tank body 4-5 of the drainer V8 The side of drainer collet 4-8, the drainer collet 4-8 are respectively equipped with cooling liquid outlet 4-7 and coolant liquid communicating pipe up and down The outlet of G1；The jacket type straight tube cooler E1 includes condensate liquid outlet tube 4-11 and is set in outside condensate liquid outlet tube 4-11 Cooling tube collet 4-10；The import of condensate liquid outlet tube 4-11 is at the tank bottom 4-9 of the solidifying tank V8 and in drainer V8 Chamber is connected；Import and the cooling liquid inlet 4-12 of coolant liquid communicating pipe G1 are respectively arranged on the cooling tube collet 4-10；
The absorption detecting unit includes absorption detecting tank V10, during the tank body 5-6 of the absorption detecting tank V10 is in Empty cylindrical shape, and the tank deck 5-2 of the absorption detecting tank V10 is provided with condensate line 5-1 and absorbs liquid pipe 5-7；
The outlet of the condensate line 5-1 is connected to the inner cavity of absorption detecting tank V10, the import of condensate line 5-1 with it is cold The outlet of lime set outlet tube 4-13 is connected, and the condensate line 5-1 is equipped with condensate liquid valve S12；
The outlet for absorbing liquid pipe 5-7 is connected to the inner cavity of absorption detecting tank V10, the import for absorbing liquid pipe 5-7 It is connected with the outlet of the outlet tube 3-5 of boric acid constant volume overflow tank V11；
It is 0.1 that the tank deck 5-2 of the absorption detecting tank V10, which is further fixed on the constant extended in absorption detecting tank V10, The tank bottom 5-5 of platinum black electrode J2, absorption detecting tank V10 are equipped with the second blender MS2；
The side of the absorption detecting tank V10 is respectively arranged with cleaning liquid pipe 5-3 and the 4th drain pipe 5-4；The cleaning The outlet of liquid pipe 5-3 is connected with the inner cavity of absorption detecting tank V10, and the import of the cleaning liquid pipe 5-3 passes through cleaning liquid pump P6 And it is connected with circuits with cleaning fluid tank V7, and the cleaning liquid pipe 5-3 is equipped with cleaning solution valve S11；
The import of the 4th drain pipe 5-4 is connected to the inner cavity of absorption detecting tank V10, the 4th drain pipe 5-4's Outlet is connected to waste liquid tank V9, and the 4th drain pipe 5-4 is equipped with absorption detecting tank waist valve S15；
The self priming pump outlet valve S2, water sample pre-process tank sampling valve S3, and water sample pretreatment tank waist valve S4, water sample are located in advance Manage tank overflow valve S5, water sample constant volume overflow tank waist valve S6, buffer valve S7, water sample constant volume overflow tank bleeder valve S8, evaporator Blow valve S9, evaporator waist valve S10, cleaning solution valve S11, condensate liquid valve S12, boric acid constant volume overflow tank bleeder valve S13, boric acid Constant volume overflow tank waist valve S14 and absorption detecting tank waist valve S15 is solenoid valve, and the electromagnetism is and PLC control unit It is respectively connected with；
The sampling pump P1, sampling pump P2, acid adding pump P3 plus alkali pump P4, buffer solution pump P5, cleaning liquid pump P6, boric acid pump P7, pH potentiometric detection electrode J1, temperature sensor TE1, the first blender MS1, the platinum black electrode J2 that constant is 0.1, second stir It mixes device MS2 and the regulator is respectively connected with PLC control unit.
Further, the second blender MS2 is magnetic-type blender.
Further, the input end of the sampling pump P1 is equipped with filter screen L.
Further, the tank deck 2-6 of the water sample pretreatment tank V1 is plane, and the tank bottom of the water sample pretreatment tank V1 is cone Shape end socket 2-8, and the first drain pipe 2-9 is arranged at the center conical head 2-8.
Further, the first blender MS1 and water sample pretreatment tank V1 coaxial arrangement.
Further, the top of the second overflow pipe 3-6 is flat mouth.
Further, the top opening and base opening of the cylinder 3-2 is threadedly coupled with top cover 3-7 and bottom cover 3-3 respectively.
Further, the drainer tank deck 4-6 is butterfly end socket, and tank bottom 4-9 is conical head.
Further, cooling liquid outlet 4-7 is connected with discharge outlet PF；Cooling liquid inlet 4-12 passes sequentially through cooling water valve The outlet end of the third outlet and sampling pump P1 of S1, water outlet pipeline a, and the cooling water valve S1 is solenoid valve, and is controlled with PLC Unit processed is connected.
Further, the second overflow pipe 3-6 is fixed on the side the cylinder 3-2, and the cylinder 3-2 is to the second overflow pipe The side 3-6 tilts 10 °~20 ° (preferably 15 °) so that the axial direction of the cylinder 3-2 and vertical direction in 10 °~20 ° (preferably Be 15 °) angle, constant volume overflow tank is tilted down about 15 degree when use, tapping rate can be accelerated but also effectively prevented The problem of only residual liquid in outlet tube can not be discharged because of surface tension of liquid further improves the accurate measurement of sampling Property；Pretreated water sample or boric acid flow into water sample constant volume overflow tank V2 or boric acid constant volume overflow tank from the first inlet tube 3-1 V11, the liquid having more are flowed out from the second overflow pipe 3-6, and the water sample or boric acid after the completion of measuring are flowed out from outlet tube 3-5.
Addition automatically is difficult to realize to solve solid pH adjusting agent, the solid pH adjusting agent of adherency is difficult to clean and solid PH adjusting agent is there are instability problems such as mutabilities, and present invention employs the buffer solutions of liquid to replace solid pH adjusting agent, And realize automatic gauge and addition.
It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic detection method, using described based on distillation-conductance The ammonia nitrogen water quality online automatic monitor of method, specifically includes:
1) start；
2) water sampling and water sample pretreatment are carried out using water sampling and pretreatment unit；
3) boric acid quantifies and absorption detecting tank V10 is added；
4) buffer quantifies and evaporator V6 is added；
5) evaporator V6 heating distillation, drainer V8 and jacket type straight tube cooler E1 condensation, absorption detecting tank V10 inhale It receives；
6) platinum black electrode J2 carries out conductance measurement, calculates ammonia nitrogen measured value later.
The principle and method of present invention application conductimetry, solution in absorption detecting tank is measured using Direct conductance Conductivity, by standard curve come Accurate Determining ammonia nitrogen concentration, eliminate in new national standard method indicator titration end-point from Deficiency in dynamic detection process.
In step 6), when the conductivity Ec detected meets the 0 μ S/cm of < Ec≤15.182, using formula (2) calculating ammonia nitrogen Concentration ρN, unit mg/L；
Ec=7.6753 ρN-0.9155(2)
When the conductivity Ec detected meets the μ S/cm of Ec > 15.182, using formula (3) calculating ammonia nitrogen concentration ρN, unit is mg/L；
Ec=5.6741 ρN+2.1632 (3)。
Compared with prior art, the beneficial effects of the present invention are:
Ammonia nitrogen water quality online automatic monitor of the invention, which solves to mix present in existing distillation-neutralization titration, to be referred to Show agent stablize that the time is short, solid pH adjusting agent is difficult to realize to add automatically, eliminates titration end-point and be difficult to it is accurate it is automatic determine and The problems such as titrimetry time is longer and technological difficulties.Solid pH adjusting agent is replaced using liquid buffer solution, realizes that pH is adjusted The automatic addition of agent；The automatic distilling apparatus adjustable using a kind of electrical heating power, distilling rate is controllable improves distillation efficiency, Increase the safety and reliability of instrument；A kind of sampling method of twoport side overflow is proposed, a kind of liquid is devised and counts automatically Device is measured, realizes the accurate quantification of water sample and absorbing liquid；Using constant is 0.1 platinum black electrode to the conductivity of solution after absorption Accurate Determining is carried out, the sensitivity and accuracy of instrument is improved, and extend the measurement range of instrument, adapts to it not only The monitoring water quality on line of the low concentrations occasion such as tap water, rivers and lakes, while the waste water for also adapting to industry and city discharge is dirty The monitoring water quality on line of the higher concentrations occasion such as water, sanitary sewage.
Detailed description of the invention
The present invention is further described with example with reference to the accompanying drawing.
Fig. 1 is overall structure diagram of the invention；
Fig. 2 is that water sample of the invention pre-processes jar structure schematic diagram；
Fig. 3 is constant volume overflow tank structural schematic diagram of the invention；
Fig. 4 is distillation unit structural schematic diagram of the invention；
Fig. 5 is absorption detecting jar structure schematic diagram of the invention；
Fig. 6 is ammonia nitrogen concentration-conductivity relation curve graph；
P1. sampling pump in Fig. 1, P2. sampling pump, P3. acid adding pump, P4. add alkali pump, P5. buffer solution pump, and P6. cleans liquid pump, P7. boric acid pumps, and V1. water sample pre-processes tank (for containing water sample to be measured), and V2. water sample constant volume overflow tank is (for containing pretreatment Water sample to be measured afterwards), V3. acid tank (for containing the dilute sulfuric acid for adjusting pH in water sample pretreatment tank), V4. alkali tank is (for containing Adjust the sodium hydroxide of pH in water sample pretreatment tank), V5. buffer fills (for containing the mixing buffering for adjusting pH in evaporator Liquid, and the cocktail buffer is by Na2HPO4Proportionally 25:2 is mixed with NaOH), V6. evaporator is (for containing wait steam Evaporate the water sample of ammonia nitrogen), V7. cleaning fluid tank (for containing the distilled water of cleaning), V8. drainer is (for the cold of steam condensation Solidifying tank), V9. waste liquid tank (waste tank after waste liquid and absorption after distillation), V10. absorption detecting tank (absorbs ammonia after distillation Tourie), V11. boric acid constant volume overflow tank (measuring tank of absorbing liquid), V12. boric acid tank (absorbing liquid boric acid storage tank), E1. folder Shell type straight tube cooler, a. water outlet pipeline, b. water sample overflow pipe, c. glass absorption tube, d. boric acid overflow pipe, S1. cooling water Valve, S2. self priming pump outlet valve, S3. water sample pre-process tank sampling valve, and S4. water sample pre-processes tank waist valve, the pretreatment of S5. water sample Tank overflow valve, S6. water sample constant volume overflow tank waist valve, S7. buffer valve, S8. water sample constant volume overflow tank bleeder valve, S9. evaporation Tank blow valve, S10. evaporator waist valve, S11. cleaning solution valve, S12. condensate liquid valve, S13. boric acid bleeder valve, S14. boric acid are fixed Hold overflow tank waist valve, S15. absorption detecting tank waist valve, the first blender of MS1., the second blender of MS2., TE1. temperature biography Sensor, J1.pH potentiometric detection electrode, the platinum black electrode that J2. constant is 0.1, L. filter screen, the mark that each solenoid valve has in Fig. 1 Note is electric control system for s's, is also the drive part of solenoid valve.
Specific embodiment
As shown in Figure 1, Figure 2, a kind of based on distillation-conductance method ammonia nitrogen water quality online auto monitoring shown in Fig. 3, Fig. 4 and Fig. 5 Instrument, including water sampling and pretreatment unit, sampling unit, distillation unit, absorption detecting unit, post-processing unit and PLC control Unit processed；And tool control module and data processing module in the PLC control unit.
The water sampling and pretreatment unit includes water sample pretreatment tank V1, the tank body of the water sample pretreatment tank V1 2-1 is in hollow cylindrical shape, and is successively arranged outlet on the tank deck 2-6 of water sample pretreatment tank V1 and pre-processes tank V1 with water sample Inner cavity the sample tap 2-5, the acid-adding port 2-3 that are connected and add alkali mouth 2-4；And the import of the acid-adding port 2-3 is pumped by acid adding P3 and be connected to acid tank V3 with circuits, described plus alkali mouth 2-4 import is by adding alkali pump P4 and matching circuits and alkali tank V4 company It is logical；
PH potentiometric detection electrode J1, temperature sensor TE1 and the first blender are equipped in the water sample pretreatment tank V1 MS1；The top on the top of the pH potentiometric detection electrode J1, the top of temperature sensor TE1 and the first blender MS1 is fixed On the tank deck of water sample pretreatment tank V1, and the bottom end of the pH potentiometric detection electrode J1, the bottom end of temperature sensor TE1 and the The bottom end of one blender MS1 all extends in water sample pretreatment tank V1；
The tank bottom 2-8 of water sample pretreatment tank V1 is equipped with the first drain pipe 2-9, the import of the first drain pipe 2-9 with The inner cavity of water sample pretreatment tank V1 is connected, and the outlet of the first drain pipe 2-9 is connected to discharge outlet PF, and the first drain pipe 2-9 It is equipped with water sample and pre-processes tank waist valve S4；
The two sides of the water sample pretreatment tank V1 are respectively equipped with water inlet pipe 2-2 and the first overflow pipe 2-7；Water inlet pipe 2-2's It exporting and is connected with the inner cavity of water sample pretreatment tank V1, the import of water inlet pipe 2-2 is connected to the first outlet of water inlet pipeline a, The import of the water inlet pipeline a is connected with the outlet of sampling pump P1, and the import of the sampling pump P1 is connected with water source, and The second outlet of the water inlet pipeline a is connected to by delivery pipe with discharge outlet PF, and the delivery pipe is discharged equipped with self priming pump Valve S2；The water inlet pipe 2-2 is equipped with water sample and pre-processes tank sampling valve S3；The import of the first overflow pipe 2-7 and water sample are pre- The inner cavity of process tank V1 is connected to, and the outlet of the first overflow pipe 2-7 is connected to discharge outlet PF, and the first overflow pipe 2-7 is equipped with water Sample pre-processes tank overflow valve S5；
The sampling unit includes water sample constant volume overflow tank V2 and boric acid constant volume overflow tank V11, and water sample constant volume overflow The tank body of tank V2 and the tank body of boric acid constant volume overflow tank V11 are cylindrical tube 3-2, and the top opening of the cylinder 3-2 and bottom Mouth is respectively provided with dismountable top cover 3-7 and bottom cover 3-3；Second drain pipe 3-4 of the inner cavity cylinder 3-2 connection；Cylinder 3-2 Two sides be respectively equipped with the first inlet tube 3-1 and outlet tube 3-5, the first inlet tube 3-1 are located at the top of outlet tube 3-5, and The outlet of one inlet tube 3-1 and the import of outlet tube 3-5 are connected to the inner cavity of cylinder 3-2；Second overflow pipe 3-6 and cylinder 3- The connection of 2 inner cavities, and the import of the second overflow pipe 3-6 is located on outlet tube 3-5；
The outlet of the second drain pipe 3-4 of the water sample constant volume overflow tank V2 is connected with discharge outlet PF, and water sample constant volume The second drain pipe 3-4 of overflow tank V2 is equipped with water sample constant volume overflow tank waist valve S6；The of the water sample constant volume overflow tank V2 The import of one inlet tube 3-1 pre-processes the outlet of the sample tap 2-5 of tank V1 by sampling pump P2 and with circuits and the water sample Connection；The outlet of the second overflow pipe 3-6 of the water sample constant volume overflow tank V2 is connected to discharge outlet PF；The water sample constant volume overflow The outlet tube 3-5 of tank V2 is equipped with water sample constant volume overflow tank bleeder valve S8；
The outlet of the second drain pipe 3-4 of the boric acid constant volume overflow tank V11 is connected with boric acid tank V12, and boric acid is fixed The the second drain pipe 3-4 for holding overflow tank V11 is equipped with boric acid constant volume overflow tank waist valve S14；The boric acid constant volume overflow tank V11 The import of the first inlet tube 3-1 P7 is pumped by boric acid and is connected to circuits with boric acid tank V12；The boric acid constant volume overflow tank The outlet tube 3-5 of V11 is equipped with boric acid bleeder valve S13；The outlet of the second overflow pipe 3-6 of the boric acid constant volume overflow tank V11 It is connected with boric acid tank V12；
The distillation unit includes evaporator V6, drainer V8 and jacket type straight tube cooler E1, the drainer V8 Positioned at the top of the evaporator V6, and the inner cavity of the evaporator V6 and the inner cavity of the drainer V8 pass through steam outlet pipe 4-4 It is connected, and steam outlet pipe 4-4 has certain length, prevents liquid bumping from buffer solution being caused to damage with the entrainment of steam It loses, and the both ends of steam outlet pipe 4-4 are connected with the tank bottom 4-9 of the tank deck 4-16 of evaporator V6 and drainer V8 respectively, and coolant liquid The both ends of communicating pipe G1 are connected with drainer V8 with jacket type straight tube cooler E1 respectively, and cooling liquid outlet 4-7 and coolant liquid Import 4-12 is connect with cooling system respectively；
The tank body 4-15 of the evaporator V6 is in hollow cylindrical shape, and the tank deck 4-16 of evaporator V6 is respectively equipped with clearly Wash pipe 4-1, the second inlet tube 4-2 and blow-down pipe 4-3；
The outlet of the cleaning pipe 4-1 is connected to the inner cavity of evaporator V6, and the import of the cleaning pipe 4-1 passes through slow respectively Fliud flushing pumps P5 and is connected with circuits, cleaning liquid pump P6 and with circuits with buffering flow container V5, cleaning fluid tank V7, and described clear Pipe 4-1 is washed equipped with buffer valve S7；
The outlet of the second inlet tube 4-2 is connected to the inner cavity of evaporator V6, the import of the second inlet tube 4-2 and water sample The outlet of the outlet tube 3-5 of constant volume overflow tank V2 is connected；
The import of the blow-down pipe 4-3 is connected to the inner cavity of evaporator V6, the outlet and ambient atmosphere of the blow-down pipe 4-3 It is connected, and blow-down pipe 4-3 is equipped with evaporator blow valve S9；
The tank bottom 4-14 of the evaporator V6 is externally provided with electric heating plate H1, and the electric heating plate H1 is connected with adjustable heating The regulator of power；The tank bottom 4-14 of evaporator V6 is additionally provided with third drain pipe 4-13, the top of third drain pipe 4-13 with The inner cavity of evaporator V6 is connected, and the bottom end insulation of third drain pipe 4-13 is connected through electric heating plate H1 and with waste liquid tank V9 It is logical, and evaporator waist valve S10 is additionally provided on third drain pipe 4-13；
The tank body 4-5 of the drainer V8 is in hollow cylindrical shape, and is arranged with outside the tank body 4-5 of the drainer V8 The side of drainer collet 4-8, the drainer collet 4-8 are respectively equipped with cooling liquid outlet 4-7 and coolant liquid communicating pipe up and down The outlet of G1；
The jacket type straight tube cooler E1 includes condensate liquid outlet tube 4-11 and is set in outside condensate liquid outlet tube 4-11 Cooling tube collet 4-10；The import of condensate liquid outlet tube 4-11 is at the tank bottom 4-9 of the solidifying tank V8 and in drainer V8 Chamber is connected；Import and the cooling liquid inlet 4-12 of coolant liquid communicating pipe G1 are respectively arranged on the cooling tube collet 4-10；
The absorption detecting unit includes absorption detecting tank V10, during the tank body 5-6 of the absorption detecting tank V10 is in Empty cylindrical shape, and the tank deck 5-2 of the absorption detecting tank V10 is provided with condensate line 5-1 and absorbs liquid pipe 5-7；
The outlet of the condensate line 5-1 is connected to the inner cavity of absorption detecting tank V10, the import of condensate line 5-1 with it is cold The outlet of lime set outlet tube 4-13 is connected, and the condensate line 5-1 is equipped with condensate liquid valve S12；
The outlet for absorbing liquid pipe 5-7 is connected to the inner cavity of absorption detecting tank V10, the import for absorbing liquid pipe 5-7 It is connected with the outlet of the outlet tube 3-5 of boric acid constant volume overflow tank V11；
It is 0.1 that the tank deck 5-2 of the absorption detecting tank V10, which is further fixed on the constant extended in absorption detecting tank V10, The tank bottom 5-5 of platinum black electrode J2, absorption detecting tank V10 are equipped with the second blender MS2；
The side of the absorption detecting tank V10 is respectively arranged with cleaning liquid pipe 5-3 and the 4th drain pipe 5-4；The cleaning The outlet of liquid pipe 5-3 is connected with the inner cavity of absorption detecting tank V10, and the import of the cleaning liquid pipe 5-3 passes through cleaning liquid pump P6 And it is connected with circuits with cleaning fluid tank V7, and the cleaning liquid pipe 5-3 is equipped with cleaning solution valve S11；
The import of the 4th drain pipe 5-4 is connected to the inner cavity of absorption detecting tank V10, the 4th drain pipe 5-4's Outlet is connected to waste liquid tank V9, and the 4th drain pipe 5-4 is equipped with absorption detecting tank waist valve S15；
The self priming pump outlet valve S2, water sample pre-process tank sampling valve S3, and water sample pretreatment tank waist valve S4, water sample are located in advance Manage tank overflow valve S5, water sample constant volume overflow tank waist valve S6, buffer valve S7, water sample constant volume overflow tank bleeder valve S8, evaporator Blow valve S9, evaporator waist valve S10, cleaning solution valve S11, condensate liquid valve S12, boric acid constant volume overflow tank bleeder valve S13, boric acid Constant volume overflow tank waist valve S14 and absorption detecting tank waist valve S15 is solenoid valve, and the electromagnetism is and PLC control unit It is respectively connected with；
The sampling pump P1, sampling pump P2, acid adding pump P3 plus alkali pump P4, buffer solution pump P5, cleaning liquid pump P6, boric acid pump P7, pH potentiometric detection electrode J1, temperature sensor TE1, the first blender MS1, the platinum black electrode J2 that constant is 0.1, second stir It mixes device MS2 and the regulator is respectively connected with PLC control unit.
The second blender MS2 is magnetic-type blender.
The input end of the sampling pump P1 is equipped with filter screen L.
The tank deck 2-6 of the water sample pretreatment tank V1 is plane, and the tank bottom of the water sample pretreatment tank V1 is conical head 2-8, and the first drain pipe 2-9 is arranged at the center conical head 2-8.
The first blender MS1 and water sample pretreatment tank V1 coaxial arrangement.
The top of the second overflow pipe 3-6 is flat mouth.
The top opening and base opening of the cylinder 3-2 is threadedly coupled with top cover 3-7 and bottom cover 3-3 respectively.
The drainer tank deck 4-6 is butterfly end socket, and tank bottom 4-9 is conical head.
Cooling liquid outlet 4-7 is connected with discharge outlet PF；Cooling liquid inlet 4-12 passes sequentially through cooling water valve S1, water outlet The third outlet of pipeline a is connected with the outlet end of sampling pump P1, and the cooling water valve S1 is solenoid valve, and controls with PLC Unit is connected.
The second overflow pipe 3-6 is fixed on the side the cylinder 3-2, and the cylinder 3-2 is to the second side overflow pipe 3-6 15 ° of inclination, so that the axial direction of the cylinder 3-2 and vertical direction are in 15 ° of angle, when use, is downward by constant volume overflow tank Constant volume overflow tank is tilted down about 15 degree when use by about 15 degree of inclination, and can accelerate tapping rate can effectively prevent again The problem of residual liquid in outlet tube can not be discharged because of surface tension of liquid further improves the accurate measurement of sampling Property；Pretreated water sample or boric acid flow into constant volume overflow tank from the first inlet tube 3-1, and the liquid having more is from the second overflow pipe 3- 6 outflows, water sample or boric acid after the completion of measuring are flowed out from outlet tube 3-5.
The syringe pump P7 is industrial formula syringe pump；The temperature sensor TE1 is Pt100 armored thermal resistance； The syringe pump P7 be industrial injection pump, the sampling pump P1 be self priming pump, sampling pump P2, acid adding pump P3, plus alkali pump P4, Buffer solution pump P5 and cleaning liquid pump P6 is peristaltic pump, and the pH potentiometric detection electrode J1 is compound pH potentiometric detection electrode； The platinum black electrode J2 is the conductance electrode that constant is 0.1.
Ammonia nitrogen water quality online automatic monitor of the invention as shown in Figures 1 to 5 includes that water sampling and pretreatment are single Member, sampling unit, distillation unit, absorption detecting unit, post-processing unit and PLC control unit.
Water sampling and pretreatment unit are by groups such as water sample pretreatment tank V1, sampling pump P1, acid adding pump P3 plus alkali pump P4 At.As shown in Fig. 2, the water sample pretreatment tank V1 is hollow cylindrical tank 2-1, the inner top surface 2-6 of tank is plane, and Tank deck 2-6 is equipped with pH potentiometric detection electrode J1, temperature sensor TE1 and the first blender MS1；Tank deck 2-6 is separately provided with sampling Mouth 2-5, acid-adding port 2-3 and plus alkali mouth 2-4；Tank side is provided with water inlet pipe 2-2 and overflow pipe 2-7；Tank bottom 2-8 is taper envelope Head, the conical head 2-8 are provided centrally with the first drain pipe 2-9.Further, the water inlet pipe 2-2, overflow pipe 2-7 Locate in advance with water sample pretreatment tank sampling valve S3, water sample pretreatment tank overflow valve S5, water sample is respectively arranged on the first drain pipe 2-9 Tank waist valve S4 is managed, the solenoid valve is connected with PLC control unit；Filter screen L, sampling pump are housed before the sampling pump P1 The water outlet pipeline a of P1 meets cooling water valve S1, self priming pump outlet valve S2 and water sample pretreatment tank sampling valve S3 respectively；Described adds Acid pump P1 pre-processes tank acid-adding port 2-3 and acid tank V3 with water sample respectively by silicone tube and is connected；Described plus alkali pump P2 passes through silicon Sebific duct adds alkali mouth 2-4 and alkali tank V4 to be connected with water sample pretreatment tank respectively.
Self priming pump outlet valve S2 is opened in water sampling and pretreatment unit starting, water sample pre-processes tank sampling valve S3 and pre- Process tank overflow valve S5, sampling pump P1 starting, water sample suck sampling pump P1 through filter screen L, and it is pre- to flow into water sample through water outlet pipeline a Process tank V1 is overflowed through overflow pipe 2-7 after hydroful, and the water sample of spilling flow to discharge outlet PF, and overflow for a period of time, closes sampling pump P1, water sample pretreatment tank overflow valve S5 and water sample pre-process tank sampling valve S3, complete water sampling.Meanwhile opening the first stirring Device MS1 detects the pH of water sample by pH electrode J1, when the pH for measuring water sample is excessive, then opens the pH that acid adding pump P3 adjusts water sample To neutrality, closes acid adding and pump P3；When the pH for measuring water sample is too small, then opens alkali pump P4 and adjusts after water sample pH is adjusted to neutrality, It closes and adds alkali pump P4.Meanwhile real time temperature signal is reached PLC control unit by temperature sensor TE1.
Sampling unit includes water sample constant volume overflow tank V2, sampling pump P2, boric acid constant volume overflow tank V11 and boric acid pump P7 etc.. As shown in figure 3, the water sample constant volume overflow tank V2 and boric acid constant volume overflow tank V11 is hollow cylindrical tube 3-2, cylinder Screwed top cover 3-7 and bottom cover 3-3 is respectively set at the top and bottom of body 3-2, the upper and lower part of the side cylinder 3-2 is set respectively It is equipped with the first inlet tube 3-1 and outlet tube 3-5, bottom cover is provided with the second drain pipe 3-4；The second overflow is provided in cylinder 3-2 Pipe 3-6, second overflow pipe is located at the side cylinder 3-2 and height is higher than the top edge of outlet tube 3-5, utilizes outlet tube 3- 5 and second overflow pipe 3-6 difference in height, accurately measure determined volume；Divide on the outlet tube 3-5 and the second drain pipe 3-4 It is not provided with water sample constant volume overflow tank waist valve S6, water sample bleeder valve S8, boric acid constant volume overflow tank waist valve S14, boric acid tapping Valve S13, the motor-driven valve are connected with PLC control unit；The sampling pump P2 is overflow with water sample constant volume respectively by silicone tube The the first inlet tube 3-1 for flowing tank is connected with water sample pretreatment tank sample tap 2-5；The described boric acid pump P7 by silicone tube respectively with Boric acid constant volume overflow tank the first inlet tube 3-1 is connected with boric acid tank V12.
After water sampling and pretreatment, PLC control unit controls boric acid pump P7 work, simultaneously closes off boric acid tapping Boric acid in valve S13 and boric acid constant volume overflow tank waist valve S14, boric acid tank V12 is transported in boric acid constant volume overflow tank V11, Liquid level rises in boric acid constant volume overflow tank V11, until overflow, the boric acid that overflow goes out is through overflow passage d (with boric acid constant volume overflow tank The second overflow pipe 3-6 connection of V11) flow back to boric acid tank V12.Boric acid pump P7 is closed in overflow after a certain period of time, then stands a timing Between after open boric acid bleeder valve S13, after the boric acid of boric acid constant volume overflow tank V11 quantification fully flows into absorption detecting tank V10 Close boric acid bleeder valve S13.Absorption detecting tank V10, which has been fed, to be closed, and PLC control unit controls sampling pump P2 work, is simultaneously closed off Water sample in water sample bleeder valve S8 and water sample constant volume overflow tank waist valve S6, water sample pretreatment tank V1 is transported to water sample constant volume and overflows Tank V2 is flowed, liquid level rises in water sample constant volume overflow tank V2, until overflow, the water sample that overflow goes out is through overflow passage b (with water sample constant volume The second overflow pipe 3-6 connection of overflow tank V2) it is discharged into discharge outlet PF.Sampling pump P2 is closed in overflow after a certain period of time, then after standing Water sample constant volume overflow tank bleeder valve S8 is opened after a certain period of time, and the water sample to water sample constant volume overflow tank V2 quantification fully flows into steaming Water sample constant volume overflow tank bleeder valve S8 is closed after sending out tank V6.
When water sample charging finishes, PLC control unit control starting buffer solution pump P5 simultaneously opens buffer valve S7, quantitative to be added dropwise Buffer solution makes water sample in evaporator V6 simultaneously close off buffer solution pump P5 in buffer valve S7 is closed after alkalescent.
The distillation unit includes evaporator V6, drainer V8 and jacket type straight tube cooler E1.As shown in figure 4, institute The both ends for coolant liquid communicating pipe G1 stated are connected with drainer V8 with jacket type straight tube cooler E1 respectively, and cooling liquid outlet 4- 7 connect with cooling system respectively with cooling liquid inlet 4-12, and the tank body 4-15 of the evaporator V6 is cylinder, tank deck 4-16 It is plane with tank bottom 4-14；The tank deck 4-16 of the evaporator V6 is provided with cleaning pipe 4-1, the second inlet tube 4-2, blow-down pipe 4-3 and steam outlet pipe 4-4, tank bottom 4-14 are provided with third drain pipe 4-13.Cleaning pipe 4-1, the second inlet tube 4-2, blow-down pipe 4-3 With buffer valve S7, water sample constant volume overflow tank bleeder valve S8, evaporator blow valve S9 are respectively arranged on third drain pipe 4-13 With evaporator waist valve S10, the solenoid valve is connected with PLC control unit；The outer bottom of evaporator V6 is provided with electric heating Disk H1, the electric heating plate H1 are connected with the regulator of adjustable heating power, and regulator is connected with PLC control unit. The drainer V8 is the cylindrical tank 4-5 for being provided with drainer collet 4-8, on the side of the drainer collet 4-8 Under be respectively arranged with the outlet of cooling liquid outlet 4-7 and coolant liquid communicating pipe G1；The drainer tank deck 4-6 is butterfly end socket, Tank bottom 4-9 is conical head, and the condensate liquid outlet tube 4-11 is located at conical head center.Coolant liquid is provided on collet 4-10 The import of communicating pipe G1 and cooling liquid inlet 4-12.
After water sample and buffer are successively quantitatively adding evaporator V6, PLC control unit control starting sampling pump P1, and Cooling water valve S1 and magnetic force the second blender MS2 is opened, while controlling regulator and heating distillation, water sample is carried out to evaporator V6 In ammonia quickly escaped with the raising of water temperature, condensed in drainer V8 after water sample boiling with water vapour, and Enter absorption detecting tank V10 through glass absorption tube c after further cooling down in jacket type straight tube cooler E1, is quantitatively adding in advance Boric acid solution absorbed.After a certain period of time, PLC control unit controls regulator and stops heating for distillation, obtains a certain amount of Distillate.
The absorption detecting unit mainly includes absorption detecting tank V10, the second blender MS2 and platinum black electrode J2.Institute The tank body 5-6 of the absorption detecting tank V10 stated is hollow cylindrical, and tank deck 5-2 and tank bottom 5-5 are plane；The absorption detecting Tank V10 tank deck 5-2 is provided with condensate line 5-1 and absorbs liquid pipe 5-7, distinguishes on the condensate line 5-1 and absorption liquid pipe 5-7 It is provided with condensate liquid valve S12 and boric acid bleeder valve S13, the solenoid valve is connected with PLC control unit；The tank deck 5-2 dress There is platinum black electrode J2, and is inserted in tank at center；The platinum black electrode J2 is the conductance electrode that constant is 0.1；Tank side is set It is equipped on cleaning liquid pipe 5-3 and the 4th drain pipe 5-4, the cleaning liquid pipe 5-3 and the 4th drain pipe 5-4 and is respectively arranged with cleaning Liquid valve S11 and absorption detecting tank waist valve S15, the solenoid valve are connected with PLC control unit；Second blender MS2 is magnetic-type blender, is placed in the bottom of absorption detecting tank V10.
When distillation unit stops heating, PLC control unit closes condensate liquid valve S12, the electricity that platinum black electrode J2 will test Conductance continually enters PLC control unit after passing through pick-up.Meanwhile PLC control unit is calculated according to the current signal after pick-up The conductivity of absorbing liquid, and then the actual content of ammonia nitrogen in water sample is calculated, and storage simultaneously and display.
The post-processing unit includes two parts of discharging of waste liquid and cleaning.After the completion of each absorption analysis, water sample Pre-process tank V1, water sample constant volume overflow tank V2, boric acid constant volume overflow tank V11, evaporator V6, the raffinate in absorption detecting tank V10 It is clean to be both needed to discharge, and is cleaned, to be analyzed to on-line sampling next time.Water sample pre-processes tank V1, water sample constant volume overflow tank The waste liquid of interior V2 is directly discharged to discharge outlet PF, and the discharging of waste liquid of V10 is to waste liquid tank V9 in evaporator V6 and absorption detecting tank.Water Sample pre-processes tank V1 and water sample constant volume overflow tank V2 and carries out prewashing with water sample to be measured, and evaporator V6 and absorption detecting tank V10 are equal Wash with distilled water, distilled water cleaning liquid pump P6 conveying.The water sample pretreatment tank V1, water sample constant volume overflow tank V2, evaporation Tank V6, absorption detecting tank V10 drain pipe on be respectively arranged with water sample pretreatment tank waist valve S4, water sample constant volume overflow tank waste liquid Valve S6, evaporator waist valve S10 and absorption detecting tank waist valve S15, the solenoid valve are connected with PLC control unit.
The post-processing of water sample constant volume overflow tank V2 is as follows: opening water sample constant volume overflow tank waist valve S6, overflows to water sample constant volume It flows tank V2 bottom drain after a certain period of time, closes water sample constant volume overflow tank waist valve S6；Start sampling pump P2, to one timing of sample introduction Between, when guaranteeing that water sample expires supreme overflow port in water sample constant volume overflow tank, sampling pump P2 is closed, and it is useless to open water sample constant volume overflow tank Liquid valve S6；After a certain period of time to the drain of water sample constant volume overflow pot bottom, water sample constant volume overflow tank waist valve S6 is closed.
The post-processing that water sample pre-processes tank V1 is identical as water sample constant volume overflow tank V2 step.
The post-processing step of evaporator V6: water sample constant volume overflow tank bleeder valve S8, evaporator blow valve S9, evaporator are opened Waist valve S10 after a certain period of time to drain closes valve water sample constant volume overflow tank bleeder valve S8, evaporator waist valve S10.It opens slow Fliud flushing liquid feed valve S7, starting cleaning liquid pump P6；After close buffer valve after extracting suitable distilled water in cleaning fluid tank V7 S8, cleaning liquid pump P6；It stands cleaning after a certain period of time, opens evaporator waist valve S10；After a certain period of time to drain, it closes and steams Send out tank waist valve S10 and evaporator blow valve S9.
The step of row's raffinate and cleaning step of absorption detecting tank V10 are with evaporator V6 is consistent.It is clear in absorption detecting tank V10 After the completion of washing, a certain amount of distilled water is extracted from cleaning fluid tank V7, for impregnating and protecting platinum black electrode J2.
Ammonia nitrogen water quality online automatic monitor of the invention automatically controls the work of other each units by PLC control unit Process, calculating, display, printing, storage detected value can also facilitate network consisting by data communication mouth progress information exchange, This instrument is controlled using remote terminal, realizes ammonia nitrogen water quality online auto monitoring.
The workflow of ammonia nitrogen water quality online automatic monitor of the invention is as follows: starting → water sampling → water sample is located in advance Reason → boric acid quantify and be added absorption detecting filling → water sample quantify and be added evaporator → buffer quantify and be added evaporator → Heat distillation, condensation, absorption → end distillation → conductance measurement → calculating ammonia nitrogen measured value → display, printing, storage measurement Value → discharging of waste liquid → cleaning → standby.
It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic detection method, using described based on distillation-conductance The ammonia nitrogen water quality online automatic monitor of method, specifically includes:
1) start；
2) water sampling and water sample pretreatment are carried out using water sampling and pretreatment unit；
3) boric acid quantifies and absorption detecting tank V10 is added；
4) buffer quantifies and evaporator V6 is added；
5) evaporator V6 heating distillation, drainer V8 and jacket type straight tube cooler E1 condensation, absorption detecting tank V10 inhale It receives；
6) platinum black electrode J2 carries out conductance measurement, calculates ammonia nitrogen measured value later.
The principle and method of present invention application conductometric analysis measure solution in absorption detecting tank using Direct conductance Conductivity eliminates in new national standard method indicator titration end-point automatic by standard curve come Accurate Determining ammonia nitrogen concentration Deficiency in detection process.
Ammonia nitrogen concentration conductance method measuring principle of the present invention are as follows: water sample to be measured under alkaline condition, one timing In, water sample is heated to boiling, is taken out of distillate with gas, is absorbed again with conductive absorbing liquid after condensing, absorbing liquid electricity The changing value of conductance is directly proportional to the drag-out of ammonia nitrogen in a certain range；The present invention is by the ammonia nitrogen solution of several normal concentrations Using distillation pretreatment mode processing, the ammonia nitrogen in distillate is absorbed with the absorbing liquid with certain conductivity, is surveyed respectively Surely the absorbing liquid conductivity before and after ammonia nitrogen is absorbed, then the conductivity of each normal concentration ammonia nitrogen solution can be indicated by formula (1) are as follows:
EcMark=Ecs-Ecb (1)
Ec in formulaMark, EcsAnd EcbRespectively the final conductivity of standard specimen, standard specimen test surveyed conductivity and blank assay is surveyed Conductivity.Then with EcMarkCorresponding standard ammonia nitrogen concentration ρNThe relationship between conductivity and ammonia nitrogen concentration is found out, and fits ammonia nitrogen Relation curve between concentration and conductivity can finally can be calculated the ammonia nitrogen concentration of water sample to be measured according to curvilinear equation. The concentration of Ammonia nitrogen standard liquid used in the present invention and the measurement data of conductivity are discrete experimental data point, need to pass through Least square method approximating method obtains the curve of continuous and derivable.
According to resulting experimental data table are as follows:
1 conductimetry blank assay result table of table
2 conductimetry standard specimen experimental result table of table
And data are carried out to fitting of a polynomial of least square on MATLAB software, matched curve is as shown in Figure 6.
According to fitting result: the ammonia nitrogen concentration ρ in low strength range (≤2mg/L)NRelationship with conductivity Ec can It is indicated with formula (2):
Ec=7.6753 ρN-0.9155(Rf=0.9999) (2)
(> 2mg/L) then can be used formula (3) to indicate in high concentration range:
Ec=5.6741 ρN+2.1632(Rf=0.9997) (3)
By the coefficient R of formula (2) and (3)fIt is found that ammonia nitrogen mass concentration and conductivity are all in entire measurement range There is good linear relationship.
For convenience of calculating and improve the detection accuracy in the case of low concentration, when the conductivity Ec detected meet 0 < Ec≤ 15.182 μ S/cm (average value of three measured values higher than average value 14.459 measured under 2mg/L concentration), using formula (2) ammonia nitrogen concentration ρ is calculatedN；
Ec=7.6753 ρN-0.9155(2)
When the conductivity Ec detected meets the μ S/cm of Ec > 15.182, using formula (3) calculating ammonia nitrogen concentration ρN；
Ec=5.6741 ρN+2.1632 (3)
The standard ammonia nitrogen solution for further preparing 0.5,1.0,2.0,5.0,10.0,16.0mg/L respectively, to each concentration Ammonia nitrogen standard specimen carries out 7 groups of parallel laboratory tests, substitutes into formula (2) and (3) calculating actual measurement ammonia nitrogen concentration after obtaining the final conductivity of standard specimen.Most The error of indication, repeatability and the stability of data are calculated according to measurement verification regulations afterwards, final result is as shown in table 3:
3 conductimetry standard solution experimental result table of table
As shown in Table 3: the maximum error of indication is 0.018mg/L to the experimental result of conductimetry in the low concentration range, Less than the regulation (± 0.2mg/L) in measurement verification regulations；The maximum error of indication in high concentration range is -3.70%, small ± 10% in measurement verification regulations.Repeated (2.878%) and stability (5.229%) are also respectively smaller than in vertification regulation The 3% of defined and 10%.
In conclusion conductimetry used in the present invention is able to satisfy ammonia nitrogen on-line computing model A class in measurement verification regulations The metering performance requirement of instrument.
Content described in this specification embodiment is only enumerating to the way of realization of inventive concept, protection of the invention Range should not be construed as being limited to the specific forms stated in the embodiments, and protection scope of the present invention also includes art technology Personnel conceive according to the present invention it is conceivable that equivalent technologies mean.

Claims (10)

1. a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, including water sampling and pretreatment unit, take Sample unit, distillation unit, absorption detecting unit, post-processing unit and PLC control unit, it is characterised in that:
The water sampling and pretreatment unit includes water sample pretreatment tank (V1), the tank body of water sample pretreatment tank (V1) (2-1) is in hollow cylindrical shape, and is successively arranged outlet on the tank deck (2-6) of water sample pretreatment tank (V1) and locates in advance with water sample Reason tank (V1) inner cavity be connected sample tap (2-5), acid-adding port (2-3) and plus alkali mouth (2-4)；And the acid-adding port (2-3) Import be connected to by acid adding pump (P3) and with circuits with sour tank (V3), the import for adding alkali mouth (2-4) is by adding alkali pump (P4) and with circuits it is connected to alkali tank (V4)；
PH potentiometric detection electrode (J1), temperature sensor (TE1) and the first stirring are equipped in water sample pretreatment tank (V1) Device (MS1)；The top of the pH potentiometric detection electrode (J1), the top of temperature sensor (TE1) and the first blender (MS1) Top is each attached on the tank deck of water sample pretreatment tank (V1), and the bottom end of the pH potentiometric detection electrode (J1), temperature sensing The bottom end of device (TE1) and the bottom end of the first blender (MS1) all extend in water sample pretreatment tank (V1)；
The tank bottom (2-8) of water sample pretreatment tank (V1) is equipped with the first drain pipe (2-9), the first drain pipe (2-9) into Mouth is connected with the inner cavity of water sample pretreatment tank (V1), and the outlet of the first drain pipe (2-9) is connected to discharge outlet (PF), and first Drain pipe (2-9) is equipped with water sample pretreatment tank waist valve (S4)；
The two sides of water sample pretreatment tank (V1) are respectively equipped with water inlet pipe (2-2) and the first overflow pipe (2-7)；Water inlet pipe (2- 2) outlet is connected with the inner cavity of water sample pretreatment tank (V1), the import of water inlet pipe (2-2) and the first of water inlet pipeline (a) The import of outlet, the water inlet pipeline (a) is connected with the outlet of sampling pump (P1), the import of the sampling pump (P1) It is connected with water source, and the second outlet of the water inlet pipeline (a) is connected to by delivery pipe with discharge outlet (PF), the discharge Pipe is equipped with self priming pump outlet valve (S2)；The water inlet pipe (2-2) is equipped with water sample pretreatment tank sampling valve (S3)；Described first The import of overflow pipe (2-7) is connected to the inner cavity of water sample pretreatment tank (V1), the outlet of the first overflow pipe (2-7) and discharge outlet (PF) it is connected to, and the first overflow pipe (2-7) is equipped with water sample pretreatment tank overflow valve (S5)；
The sampling unit includes water sample constant volume overflow tank (V2) and boric acid constant volume overflow tank (V11), and water sample constant volume overflow The tank body of tank (V2) and the tank body of boric acid constant volume overflow tank (V11) are cylindrical tube (3-2), and the cylinder (3-2) Top opening and base opening are respectively provided with dismountable top cover (3-7) and bottom cover (3-3)；The second row of the cylinder inner cavity (3-2) connection Liquid pipe (3-4)；The two sides of cylinder (3-2) are respectively equipped with the first inlet tube (3-1) and outlet tube (3-5), the first inlet tube (3-1) Positioned at the top of outlet tube (3-5), and the first inlet tube (3-1) outlet and outlet tube (3-5) import with cylinder (3-2) Inner cavity connection；Second overflow pipe (3-6) is connected to the inner cavity cylinder (3-2), and the import of the second overflow pipe (3-6) is located at liquid It manages on (3-5)；
The outlet of the second drain pipe (3-4) of the water sample constant volume overflow tank (V2) is connected with discharge outlet (PF), and water sample is fixed The second drain pipe (3-4) for holding overflow tank (V2) is equipped with water sample constant volume overflow tank waist valve (S6)；The water sample constant volume overflow The import of the first inlet tube (3-1) of tank (V2) pre-processes tank (V1) by sampling pump (P2) and with circuits and the water sample The outlet of sample tap (2-5)；The bottom end of the second overflow pipe (3-6) of the water sample constant volume overflow tank (V2) and discharge outlet (PF) it is connected to；The outlet tube (3-5) of the water sample constant volume overflow tank (V2) is equipped with water sample constant volume overflow tank bleeder valve (S8)；
The outlet of the second drain pipe (3-4) of the boric acid constant volume overflow tank (V11) is connected with boric acid tank (V12), and boric acid The second drain pipe (3-4) of constant volume overflow tank (V11) is equipped with boric acid constant volume overflow tank waist valve (S14)；The boric acid constant volume The import of the first inlet tube (3-1) of overflow tank (V11) is connected by boric acid pump (P7) and with circuits with boric acid tank (V12) It is logical；The outlet tube (3-5) of the boric acid constant volume overflow tank (V11) is equipped with boric acid bleeder valve (S13)；The boric acid constant volume overflow The bottom end of the second overflow pipe (3-6) of tank (V11) is connected with boric acid tank (V12)；
The distillation unit includes evaporator (V6), drainer (V8) and jacket type straight tube cooler (E1), the drainer (V8) it is located at the top of the evaporator (V6), and the inner cavity of the evaporator (V6) and the inner cavity of the drainer (V8) pass through Steam outlet pipe (4-4) is connected, and the both ends of steam outlet pipe (4-4) respectively with the tank deck (4-16) of evaporator (V6) and drainer (V8) Tank bottom (4-9) be connected, and the both ends of coolant liquid communicating pipe (G1) respectively with drainer (V8) and jacket type straight tube cooler (E1) it is connected, and the cooling liquid outlet (4-7) and cooling liquid inlet (4-12) are connected with cooling system；
The tank body (4-15) of the evaporator (V6) is in hollow cylindrical shape, and the tank deck (4-16) of evaporator (V6) is respectively Equipped with cleaning pipe (4-1), the second inlet tube (4-2) and blow-down pipe (4-3)；
The outlet of the cleaning pipe (4-1) is connected to the inner cavity of evaporator (V6), and the import of the cleaning pipe (4-1) passes through respectively Buffer solution pump (P5) and it is connected with circuits, cleaning liquid pump (P6) and with circuits with flow container (V5), cleaning fluid tank (V7) is buffered It is logical, and the cleaning pipe (4-1) is equipped with buffer valve (S7)；
The outlet of second inlet tube (4-2) is connected to the inner cavity of evaporator (V6), the import of the second inlet tube (4-2) and water The outlet of the outlet tube (3-5) of sample constant volume overflow tank (V2) is connected；
The import of the blow-down pipe (4-3) is connected to the inner cavity of evaporator (V6), and the outlet of the blow-down pipe (4-3) and the external world are big Gas phase connection, and blow-down pipe (4-3) is equipped with evaporator blow valve (S9)；
The tank bottom (4-14) of the evaporator (V6) is externally provided with electric heating plate (H1), and the electric heating plate (H1) is connected with adjustable The regulator of heating power；The tank bottom (4-14) of evaporator (V6) is additionally provided with third drain pipe (4-13), third drain pipe (4- 13) top is connected with the inner cavity of evaporator (V6), and the bottom end insulation of third drain pipe (4-13) runs through electric heating plate (H1) And it is connected with waste liquid tank (V9), and evaporator waist valve (S10) is additionally provided on third drain pipe (4-13)；
The tank body (4-5) of the drainer (V8) is in hollow cylindrical shape, and tank body (4-5) housing of the drainer (V8) Equipped with drainer collet (4-8), the side of the drainer collet (4-8) is respectively equipped with cooling liquid outlet (4-7) and cold up and down But the outlet of liquid communicating pipe (G1)；
The jacket type straight tube cooler (E1) includes condensate liquid outlet tube (4-11) and is set in condensate liquid outlet tube (4-11) Outer cooling tube collet (4-10)；The import of condensate liquid outlet tube (4-11) at the tank bottom (4-9) of the drainer (V8) with The inner cavity of drainer (V8) is connected；The import of coolant liquid communicating pipe (G1) is respectively arranged on the cooling tube collet (4-10) With cooling liquid inlet (4-12)；
The absorption detecting unit includes absorption detecting tank (V10), and the tank body (5-6) of the absorption detecting tank (V10) is in Hollow cylindrical shape, and the tank deck (5-2) of the absorption detecting tank (V10) is provided with condensate line (5-1) and absorbs liquid pipe (5-7)；
The outlet of the condensate line (5-1) is connected to the inner cavity of absorption detecting tank (V10), the import of condensate line (5-1) with The outlet of condensate liquid outlet tube (4-13) is connected, and the condensate line (5-1) is equipped with condensate liquid valve (S12)；
It is described absorb liquid pipe (5-7) outlet be connected to the inner cavity of absorption detecting tank (V10), it is described absorption liquid pipe (5-7) into Mouth is connected with the outlet of the outlet tube (3-5) of boric acid constant volume overflow tank (V11)；
The tank deck (5-2) of the absorption detecting tank (V10) is further fixed on the platinum black electrode extended in absorption detecting tank (V10) (J2), the tank bottom (5-5) of absorption detecting tank (V10) is equipped with the second blender (MS2)；
The side of the absorption detecting tank (V10) is respectively arranged with cleaning liquid pipe (5-3) and the 4th drain pipe (5-4)；It is described clear The outlet of lotion pipeline (5-3) is connected with the inner cavity of absorption detecting tank (V10), and the import of cleaning liquid pipe (5-3) passes through clear Lotion pumps (P6) and it is connected with cleaning fluid tank (V7) with circuits, and the cleaning liquid pipe (5-3) is equipped with cleaning solution valve (S11)；
The import of 4th drain pipe (5-4) is connected to the inner cavity of absorption detecting tank (V10), the 4th drain pipe (5-4) Outlet be connected to waste liquid tank (V9), and the 4th drain pipe (5-4) be equipped with absorption detecting tank waist valve (S15)；
The self priming pump outlet valve (S2), water sample pretreatment tank sampling valve (S3), water sample pretreatment tank waist valve (S4), water sample are pre- Process tank overflow valve (S5), water sample constant volume overflow tank waist valve (S6), buffer valve (S7), water sample constant volume overflow tank bleeder valve (S8), evaporator blow valve (S9), evaporator waist valve (S10), cleaning solution valve (S11), condensate liquid valve (S12), boric acid tapping Valve (S13), boric acid constant volume overflow tank waist valve (S14) and absorption detecting tank waist valve (S15) are solenoid valve, and the electromagnetism It is respectively connected with PLC control unit；
The sampling pump (P1), sampling pump (P2), acid adding pump (P3) plus alkali pump (P4), buffer solution pump (P5), cleaning liquid pump (P6), boric acid pumps (P7), pH potentiometric detection electrode (J1), temperature sensor (TE1), the first blender (MS1), platinum black electrode (J2), the second blender (MS2) and the regulator are respectively connected with PLC control unit.
2. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: second blender (MS2) is magnetic-type blender.
3. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: the input end of the sampling pump (P1) is equipped with filter screen (L).
4. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: the tank deck (2-6) of water sample pretreatment tank (V1) is plane, and the tank bottom of water sample pretreatment tank (V1) is conical head (2-8), and the first drain pipe (2-9) is arranged at the center the conical head (2-8).
5. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: the top opening and base opening of the cylinder (3-2) are threadedly coupled with top cover (3-7) and bottom cover (3-3) respectively.
6. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: the drainer tank deck (4-6) is butterfly end socket, and tank bottom (4-9) is conical head.
7. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists In: the cooling liquid outlet (4-7) is connected with discharge outlet (PF)；Cooling liquid inlet (4-12) passes sequentially through cooling water valve (S1), the third outlet of water outlet pipeline (a) is connected with the outlet end of sampling pump (P1), and the cooling water valve (S1) is electricity Magnet valve, the cooling water valve (S1) are connected with PLC control unit.
8. as described in claim 1 a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, feature exists The side the cylinder (3-2) is fixed in: second overflow pipe (3-6), and the cylinder (3-2) is to the second overflow pipe (3-6) Side tilts 10 °~20 °, so that the axial direction of the cylinder (3-2) and vertical direction are in 10 °~20 ° of angle, it is pretreated Water sample or boric acid have more from the first inlet tube (3-1) inflow water sample constant volume overflow tank (V2) or boric acid constant volume overflow tank (V11) Liquid is flowed out from the second overflow pipe (3-6), and the water sample or boric acid after the completion of measuring are flowed out from outlet tube (3-5).
9. a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic detection method, which is characterized in that using such as claim 1~8 is described in any item based on distillation-conductance method ammonia nitrogen water quality online automatic monitor, specifically include:
1) start；
2) water sampling and water sample pretreatment are carried out using water sampling and pretreatment unit；
3) boric acid quantifies and absorption detecting tank (V10) is added；
4) buffer quantifies and evaporator (V6) is added；
5) evaporator (V6) heating distillation, drainer (V8) and jacket type straight tube cooler (E1) condensation, absorption detecting tank (V10) It absorbs；
6) platinum black electrode (J2) carries out conductance measurement, calculates ammonia nitrogen measured value later.
10. according to claim 9 based on distillation-conductance method ammonia nitrogen water quality online automatic detection method, feature exists In in step 6), when the conductivity Ec detected meets the 0 μ S/cm of < Ec≤15.182, using formula (2) calculating ammonia nitrogen concentration ρN, unit mg/L；
Ec=7.6753 ρN-0.9155 (2)
When the conductivity Ec detected meets the μ S/cm of Ec > 15.182, using formula (3) calculating ammonia nitrogen concentration ρN, unit mg/L；
Ec=5.6741 ρN+2.1632 (3)。
CN201811177631.5A 2018-10-10 2018-10-10 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method Pending CN108982597A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811177631.5A CN108982597A (en) 2018-10-10 2018-10-10 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811177631.5A CN108982597A (en) 2018-10-10 2018-10-10 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method

Publications (1)

Publication Number Publication Date
CN108982597A true CN108982597A (en) 2018-12-11

Family

ID=64543418

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811177631.5A Pending CN108982597A (en) 2018-10-10 2018-10-10 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method

Country Status (1)

Country Link
CN (1) CN108982597A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111024794A (en) * 2019-12-31 2020-04-17 常州市深水城北污水处理有限公司 Continuous monitor for nitrate nitrogen in water and operation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004188268A (en) * 2002-12-09 2004-07-08 Toshiba Corp Water quality monitoring/controlling apparatus and sewage treating system
CN201126435Y (en) * 2007-11-12 2008-10-01 江苏绿叶环保科技仪器有限公司 Ammonia nitrogen automatic detection instrument
CN103245697A (en) * 2013-04-18 2013-08-14 姜堰市华晨仪器有限公司 Ammonia nitrogen on-line monitoring instrument
CN205150787U (en) * 2015-10-23 2016-04-13 克拉玛依新科澳石油天然气技术股份有限公司 Fluid reservoir is joined in marriage to improved generation convenient to from complete flowing back of liquid outlet
CN107515272A (en) * 2017-08-30 2017-12-26 浙江工业大学 A kind of ammonia nitrogen on-line computing model based on distillation titration
CN209215275U (en) * 2018-10-10 2019-08-06 浙江工业大学 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004188268A (en) * 2002-12-09 2004-07-08 Toshiba Corp Water quality monitoring/controlling apparatus and sewage treating system
CN201126435Y (en) * 2007-11-12 2008-10-01 江苏绿叶环保科技仪器有限公司 Ammonia nitrogen automatic detection instrument
CN103245697A (en) * 2013-04-18 2013-08-14 姜堰市华晨仪器有限公司 Ammonia nitrogen on-line monitoring instrument
CN205150787U (en) * 2015-10-23 2016-04-13 克拉玛依新科澳石油天然气技术股份有限公司 Fluid reservoir is joined in marriage to improved generation convenient to from complete flowing back of liquid outlet
CN107515272A (en) * 2017-08-30 2017-12-26 浙江工业大学 A kind of ammonia nitrogen on-line computing model based on distillation titration
CN209215275U (en) * 2018-10-10 2019-08-06 浙江工业大学 It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈静;徐滋秋;付万年;徐惠忠;: "电导法氨氮自动连续监测仪的设计与研究", 仪表技术, no. 12, pages 39 - 41 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111024794A (en) * 2019-12-31 2020-04-17 常州市深水城北污水处理有限公司 Continuous monitor for nitrate nitrogen in water and operation method thereof

Similar Documents

Publication Publication Date Title
CN209215275U (en) It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor
CN206431040U (en) A kind of Automatic On-line ammonia Nitrogen Analyzer
CN107515272B (en) Ammonia nitrogen on-line monitoring appearance based on distillation-titration method
CN207557094U (en) A kind of permanganate index on-line computing model
CN108043059B (en) Rotary evaporator capable of accurately realizing quantification of concentrated solution
CN102338805A (en) Instrument and method for automatically analyzing ammonia nitrogen in laboratory
CN219608910U (en) Water quality monitoring device based on quantitative concentration
CN105738361B (en) Permanganate index automatic analyzer and analysis method in water
CN207336460U (en) A kind of ammonia nitrogen on-line computing model based on distillation titration method
CN108982597A (en) It is a kind of based on distillation-conductance method ammonia nitrogen water quality online automatic monitor and method
CN107727593A (en) A kind of system and method for total nitrogen in measure water quality
CN210166315U (en) Full-automatic COD analytical equipment
KR102156150B1 (en) METHOD AND APPARATUS FOR MEASURING TOTAL ORGANIC CARBON BY COMBUSTION OXIDATION USING PROPORTIONAl CONTROL SAMPLE PRECISION INJECTION METHOD AND DOUBLE COOLING GAS-LIQUID SEPARATION
CN205562574U (en) Aquatic permanganate index autoanalyzer
CN209589919U (en) A kind of conductivity detector with temperature adjustment function
CN203337556U (en) Titration cell and detection device for detecting acid value of petroleum product by using reflowing method
CN206804530U (en) A kind of sea water COD determines device
CN103940809B (en) Steam quality testing arrangement and method of testing thereof
CN212391324U (en) Constant temperature heating sample digestion device
CN209028052U (en) A kind of high-precision titrator of multipurpose high load
CN214374318U (en) Device for detecting COD content in water
CN109632449A (en) A kind of traditional Chinese drug inspissation technical process medical fluid density on-line detecting system and detection method
CN217717183U (en) Diluting device used inside automatic online water quality monitor
CN204556487U (en) A kind of ammonia nitrogen on-line computing model Metal constant temperature measuring chamber of variable light path
CN206192891U (en) Online real -time detection device of oxide always remains

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination