CN106645614A - A seawater total alkalinity on-line monitoring system - Google Patents
A seawater total alkalinity on-line monitoring system Download PDFInfo
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- CN106645614A CN106645614A CN201610990352.5A CN201610990352A CN106645614A CN 106645614 A CN106645614 A CN 106645614A CN 201610990352 A CN201610990352 A CN 201610990352A CN 106645614 A CN106645614 A CN 106645614A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
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Abstract
The invention belongs to the technical field of sea monitoring, and particularly relates to an instrument which can be used for seawater total alkalinity on-line monitoring. A seawater total alkalinity on-line monitoring system mainly comprises a flow path system, a monitoring device and a control system. The flow path system is used for completing sample injection, titration, calibration, waste discharging and washing processes of a seawater sample. The monitoring device is connected to the flow path system, and is used for monitoring the solution state of the flow path system, and sending monitored temperature, salinity and pH data to the control system. The control system is connected to the flow path system and the monitoring device, and is used for controlling the flow path system, processing the data sent by the monitoring device, completing on-line monitoring and outputting the monitoring result of the seawater total alkalinity to the outside. The on-line monitoring system can achieve on-line monitoring and analysis of the seawater total alkalinity, does not need manual operation, and is highly automatic and high in measurement precision.
Description
Technical field
The invention belongs to marine monitoring technology field, and in particular to a kind of instrument that can be used for sea water total alkalinity on-line monitoring
Equipment.
Background technology
Total alkalinity (Total Alkalinity, TA) is an important parameter for characterizing sea water carbonate system, is accurately surveyed
Dinghai water TA is significant to understanding the marine biogeochemistry processes such as ocean Carbon cycle, sea water acidifying.Sea water total alkalinity
Assay method mainly have single-point pH algoscopys, iodimetric titration, neutralization titration and pH potentiometric titrations etc..Compared to other
Method, potentiometric titration is widely used because of precision and accuracy highest.China's ocean industry standard《HY/T 178-
The measure of 2014 alkalinity of seawater》The assay method of middle recommendation is both pH potentiometric titrations.The sea water total alkalinity instrument commonly used at present
Mainly there are the AS-ALK2 of Apollo companies of the U.S., a VINDTA 3S of German Marianda, and the Kimoto companies of Japan
ATT-15 etc., above product is all based on potentiometric titration design, but is only capable of in experiment indoor application, it is impossible to completes sea water and exists
Line analysis is monitored.The domestic total alkalinity measurer for mainly having an Xiamen University currently for sea water total alkalinity in-situ monitoring（Patent
Publication number：CN101221131）, the device accurately determines pH using photometry, then calculates and obtains total alkali angle value, equivalent to pH
Single-point method.Separately there is total alkalinity online testing device（Authorization Notice No.：CN 201926626 U）Although the device can complete alkali
The on-line monitoring of degree, but limited by method, the accuracy and precision of device be not high, and does not relate to seawater salinity
To H+The impact of the factors such as activity, therefore it is unsuitable for the analysis of seawater sample.Not yet having at present more ripe can complete sea
The instrument of water total alkalinity on-line measurement.
The content of the invention
Not enough for existing instrument, the present invention is based on pH potentiometric titration principles, there is provided a kind of high degree of automation, response
The sea water total alkalinity on-line measurement system that time is short, precision accuracy is good, it is adaptable to the long-term online reality of sea water total alkalinity
When research and application.Meanwhile, the correction of trip temperature and salinity, the instrument of the present invention are entered by the seawater salinity sensor of instrument internal
It is equally applicable to the more serious region of river mouth and seawater pollution.
The technical solution used in the present invention is：A kind of sea water total alkalinity on-line monitoring system, mainly including flow path system, prison
Survey device and control system；Described flow path system is used to complete sample introduction, titration, calibration, waste discharge, the flushing of sea water sample
Process；Described monitoring device is connected with flow path system, for monitoring the solution state of flow path system, and by the temperature for monitoring
Degree, salinity, pH data is activations are to control system；Described control system is connected with flow path system and monitoring device system, is used for
The work of flow path system is controlled, and the data that monitoring device is transmitted are processed, and complete on-line monitoring, externally output sea water is total
The monitoring result of basicity.
Described flow path system include reaction tank, sampling device, pH buffer solution calibrating installations, reaction tank cleaning device,
Agitating device, waste discharge and waste collecting device；Described sampling device, pH buffer solution calibrating installations, reaction tank cleaning device
And waste discharge and waste collecting device are connected with reaction tank；Agitating device is arranged on reaction tank bottom.
Described sampling device includes sea water sample sampling device and HCl solution sampling device.
Sea water sample sampling device is made up of plunger displacement pump, multiple-way valve and pipeline, completes sampling, and seawater sample injection is reacted
Pond.
HCl solution sampling device adopts plunger displacement pump, extracts HCl solution, injects reaction tank, completes to titrate work.
Described pH buffer solution calibrating installation is made up of peristaltic pump and multiple-way valve, successively by different pH buffer solution schools
It is accurate（It is various）Injection reaction tank, carries out the calibration of pH/ potential measurement systems.
Described reaction tank cleaning device is made up of peristaltic pump and multiple-way valve, for flushing liquor to be injected into reaction tank, is being stirred
Cleaning is completed under the stirring for mixing device.Meanwhile, the plunger that cleanout fluid completes sea water sample sampling device can be switched by multiple-way valve
The cleaning of pump.In addition, by reaction tank cleaning device, also electrode soak can be injected into reaction tank, keep in the gap of measurement
The moistening of electrode, with long-time electrode is preserved, and realizes that pH electrode is safeguarded.
Described agitating device includes electromagnetic mixing apparatus and stirring magneton.
Described waste discharge and waste collecting device is made up of electromagnetic valve, peristaltic pump and waste liquid tank, by the waste liquid in reaction tank
Waste liquid tank is expelled to, to recycle.
Described monitoring device includes thermohaline sensor and pH/ potential electrodes, and described pH/ potential electrodes can be to H+Quickly
Response, can continuously monitor on-line for a long time after primary calibration, without the need for frequent maintenance, be adapted to on-line monitoring.Sense by more than
Device monitors flow path system solution state, and monitoring system is by data is activations such as temperature, salinity, pH to machine system.
Described control system completes calibration, sample introduction, drop by the plunger displacement pump of control flow path system, peristaltic pump, electromagnetic valve
Fixed, waste discharge, the process rinsed；Simultaneously the data message that the HCl volumes of record and monitoring device are transmitted is carried out into data processing, led to
Cross the volume that built-in Gran mapping processing routine judges the HCl of titration end-point, in addition temperature and salt correction, calculate out sea water total
The numerical value of basicity, completes on-line monitoring, externally the monitoring result of output sea water total alkalinity.
The sea water total alkalinity on-line monitoring system of the present invention, it is possible to achieve the on-line monitoring analysis of sea water total alkalinity, without the need for
Artificial operation, increasingly automated, certainty of measurement is high, can be integrated in large-scale on-line monitoring system, the such as station, buoy.And
The system has modular feature, can independently arrange in pairs or groups, wide accommodation.
Description of the drawings
Fig. 1 is the structure chart of the sea water total alkalinity on-line monitoring system of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples the sea water total alkalinity on-line monitoring system of the present invention is described in detail and is explained
State.
As shown in figure 1, the sea water total alkalinity on-line monitoring system of invention, mainly by flow path system, monitoring device and control
System composition processed.
Flow path system includes reaction tank 1, the first multiple-way valve 2, the first plunger displacement pump 3, the second plunger displacement pump 4, electromagnetic mixing apparatus
7th, the first peristaltic pump 8, the second multiple-way valve 9, the second peristaltic pump 10, the 3rd multiple-way valve 11, the 3rd peristaltic pump 12, waste liquid tank 13,
One electromagnetic valve 14 and the second electromagnetic valve 15.
Reaction tank 1 is the reaction vessel of the processes such as system calibration, titration, by the quartz glass of firm super-hydrophobic oleophobic property
Material completes.One piece of magneton is placed in reaction tank inside, during reaction in the presence of electromagnetic mixing apparatus 7, completes Beater operator
Make.
The sea water sample being made up of the first plunger displacement pump 3, the first multiple-way valve 2, the first electromagnetic valve 14 and polyfluortetraethylene pipe enters
Sampling device, completes high precisely sampling, and seawater sample is injected in reaction tank 1.
The HCl solution sampling device being made up of the second plunger displacement pump 4, can accurately extract HCl solution（About 0.100 mol/L, carries
Front Na2CO3Standardization of solution）, under control of the control system, in having the injection reaction tank 1 of step, complete to titrate work.
The reaction tank cleaning device being made up of the first peristaltic pump 8 and the second multiple-way valve 9 is by flushing liquor（Low CO2Content）Injection
Reaction tank, completes cleaning under the stirring of magneton and electromagnetic mixing apparatus.Meanwhile, cleanout fluid can be switched by the first multiple-way valve 2
Complete the cleaning of the first plunger displacement pump 3.
Reaction tank cleaning device again can be as pH electrode attending device, by the first peristaltic pump 8 and the second multiple-way valve 9 by electricity
Pole soak injection reaction tank 1, in the moistening of the gap holding electrode of measurement, with long-time electrode is preserved.
The pH buffer solution calibrating installation being made up of the second peristaltic pump 10 and the 3rd multiple-way valve 11 successively delays different pH
Rush solution calibration（It is various）In injection reaction tank 1, the calibration of pH/ potential measurement systems is carried out.
Waste liquid tank 13 is connected with reaction tank, is arranged the waste liquid in reaction tank by the second electromagnetic valve 14 and the 3rd peristaltic pump 12
Go out to waste liquid tank, to recycle.
Monitoring device is made up of high accuracy thermohaline sensor 6 and high accuracy pH/ potential electrode 5, pH/ potential electrodes used
5 can be to H+Quick response, can continuously monitor on-line for a long time after primary calibration, without the need for frequent maintenance, be adapted to on-line monitoring.It is logical
Above Sensor monitoring flow path system solution state is crossed, the data is activations such as temperature, salinity, pH are by monitoring system to the control of whole machine
System.
High accuracy number plunger displacement pump, high precision peristaltic pump, multiple-way valve, electromagnetic valve that control system passes through control flow path system
Etc. the process for completing calibration, sample introduction, titration, waste discharge, flushing；The data for simultaneously transmitting the HCl volumes of record and monitoring device
Information carries out data processing, the volume of the HCl of titration end-point is judged by modes such as Gran mappings, second differentials, in addition temperature
And salt correction, the numerical value of sea water total alkalinity is calculated out, on-line monitoring is completed, externally the monitoring result of output sea water total alkalinity.
Plunger displacement pump in flow path system adopts high accuracy number plunger displacement pump, and peristaltic pump is high precision peristaltic pump.
The sea water total alkalinity on-line monitoring system of the present invention, its first test process is as follows：
1st, removal waste fluid：Using front, there is pH electrode soak in reaction tank 1, it is therefore desirable to discharge and rinse, by the second electromagnetic valve
15 and the 3rd peristaltic pump 12 drain liquid in reaction tank.
2nd, rinse：Flushing liquor injects reaction tank 1 by the first multiple-way valve 2 by the first plunger displacement pump 3 and the first electromagnetic valve 14,
The flushing of the first plunger displacement pump 3 and reaction tank is completed in the presence of electromagnetic mixing apparatus 7 and magneton, the second electromagnetic valve 15 and the 3rd is compacted
The control discharge of dynamic pump 12.
3rd, calibrate：PH buffer solution is implanted sequentially under the control of the second peristaltic pump 10 and the 3rd multiple-way valve 11, and to carry out pH electric
Pole is calibrated, and after the completion of calibration, the second electromagnetic valve 15 and the control of the 3rd peristaltic pump 12 are discharged.
4th, sea water sample injects reaction tank by the first plunger displacement pump 3 and the first electromagnetic valve 14, then discharges.
5th, flushing liquor injects reaction tank by the first peristaltic pump 8 by the second multiple-way valve 9, in electromagnetic mixing apparatus 7 and magneton
In the presence of complete the flushing of reaction tank, pH/ points position electrode 5 and thermohaline sensor 6.Solution conductivity is monitored by thermohaline sensor
Rate changes, and checks whether pipeline is rinsed well with reaction tank.
6th, sea water sample injects reaction tank by the first multiple-way valve 2 by the first plunger displacement pump 3, by the slow note of the second plunger displacement pump 4
Enter HCl, record adds the volume of HCl solution, while pH/ potential electrodes and temperature, the change of salinity sensor are monitored, it is excessive
PH is titrated to for 2.50.Control system is by VHClWith the mapping of pH/ potential datas, by the process of built-in Gran plotting programs, dripped
The data of terminal are determined, while according to the monitoring result of thermohaline sensor, final Inversion Calculation goes out total alkalinity numerical value.
During first measurement, three titration can be carried out, when the result error of three measure is less than 0.2%, whole on-line monitoring system
System can be continued to run with according to setting.If result error is larger, electrode is recalibrated, and repeat to titrate, until three results are inclined
Difference is less than 0.2%.
It is qualified to monitor for the first time, and whole on-line monitoring system monitors sea water total alkalinity according to automatic running is arranged.
During system continuous monitoring, complete once to monitor according to 4 → 5 → 6 order.If there is abnormal, system report in result
It is alert.
After completing test, flushing liquor injects reaction tank by the first multiple-way valve 2 by the first plunger displacement pump 3, makees in electromagnetic agitation
Flow path system flushing is completed with.By the first peristaltic pump 8 and the second multiple-way valve 9, electrode soak injects reaction tank to protect
Electrode.
Because the pH/ potential electrodes that adopt are for the pH electrode of high stability, without the need for frequent calibration.The situation of long-time application
Under, system irregularly will be calibrated before test sample according to test frequency, sea state and using arranging to pH electrode.
Claims (8)
1. a kind of sea water total alkalinity on-line monitoring system, it is characterised in that：Mainly include flow path system, monitoring device and control
System processed；Described flow path system is used to complete sample introduction, titration, calibration, waste discharge, the flushing process of sea water sample；Described prison
Survey device to be connected with flow path system, for monitoring the solution state of flow path system, and by the temperature for monitoring, salinity, pH data
Send to control system；Described control system is connected with flow path system and monitoring device, for controlling the work of flow path system,
And the data for transmitting monitoring device are processed, on-line monitoring is completed, externally the monitoring result of output sea water total alkalinity.
2. sea water total alkalinity on-line monitoring system according to claim 1, it is characterised in that：Described flow path system includes
Reaction tank, sampling device, pH buffer solution calibrating installations, reaction tank cleaning device, agitating device, waste discharge and waste collection dress
Put；Described sampling device, pH buffer solution calibrating installations, reaction tank cleaning device and waste discharge and waste collecting device with instead
Pond is answered to connect；Agitating device is arranged on reaction tank bottom.
3. sea water total alkalinity on-line monitoring system according to claim 2, it is characterised in that：Described sampling device is main
It is made up of plunger displacement pump, including sea water sample sampling device and HCl solution sampling device.
4. sea water total alkalinity on-line monitoring system according to claim 3, it is characterised in that：Described sea water sample sample introduction
Device also includes multiple-way valve, electromagnetic valve.
5. sea water total alkalinity on-line monitoring system according to claim 2, it is characterised in that：Described pH buffer solution school
Standard apparatus and reaction tank cleaning device are constituted by peristaltic pump and multiple-way valve.
6. sea water total alkalinity on-line monitoring system according to claim 2, it is characterised in that：Described agitating device includes
Electromagnetic mixing apparatus and stirring magneton.
7. sea water total alkalinity on-line monitoring system according to claim 2, it is characterised in that：Described waste discharge and waste liquid is received
Acquisition means are made up of electromagnetic valve, peristaltic pump and waste liquid tank, and the waste liquid in reaction tank is expelled to into waste liquid tank, to recycle.
8. the sea water total alkalinity on-line monitoring system according to any one of claim 1-7, it is characterised in that：Described monitoring
Device includes thermohaline sensor and pH/ potential electrodes.
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| CN201610990352.5A CN106645614A (en) | 2016-11-10 | 2016-11-10 | A seawater total alkalinity on-line monitoring system |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111678966A (en) * | 2020-05-25 | 2020-09-18 | 中国科学院烟台海岸带研究所 | Electrochemical sensing-based ocean carbon dioxide on-line monitoring method and device |
| CN112485315A (en) * | 2020-11-10 | 2021-03-12 | 西安西热水务环保有限公司 | High-hardness wastewater scaling ion online monitoring system and method |
| CN112858425A (en) * | 2021-01-18 | 2021-05-28 | 江西力沃德科技有限公司 | Acidity analyzer |
| CN112897471A (en) * | 2021-01-08 | 2021-06-04 | 黎明化工研究设计院有限责任公司 | Online analysis equipment for alkalinity of working solution in preparation of hydrogen peroxide by anthraquinone process and application method thereof |
| TWI744097B (en) * | 2020-11-18 | 2021-10-21 | 包天一 | Seawater alkalinity detection system |
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| CN112897471A (en) * | 2021-01-08 | 2021-06-04 | 黎明化工研究设计院有限责任公司 | Online analysis equipment for alkalinity of working solution in preparation of hydrogen peroxide by anthraquinone process and application method thereof |
| CN112858425A (en) * | 2021-01-18 | 2021-05-28 | 江西力沃德科技有限公司 | Acidity analyzer |
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Address after: 266200, Qingdao, Shandong, Qingdao, Qingdao, the core of the blue Silicon Valley, blue Silicon Valley business center, phase one, building No. 1. Applicant after: Inst. of Marine Apparatus & Instruments, Shandong Prov. Academy of Sciences Address before: 266071 Shandong city of Qingdao province Zhejiang City Road No. 28 Applicant before: Inst. of Marine Apparatus & Instruments, Shandong Prov. Academy of Sciences |
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Application publication date: 20170510 |