CN107305194B - A kind of heavy metal detector and its electrolytic cell - Google Patents
A kind of heavy metal detector and its electrolytic cell Download PDFInfo
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- CN107305194B CN107305194B CN201610252388.3A CN201610252388A CN107305194B CN 107305194 B CN107305194 B CN 107305194B CN 201610252388 A CN201610252388 A CN 201610252388A CN 107305194 B CN107305194 B CN 107305194B
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- G—PHYSICS
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G—PHYSICS
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- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
A kind of heavy metal analysis electrolytic cell, when carrying out the concentration stage of Electrochemical Detection, conversion circuit exports constant voltage to auxiliary electrode, when carrying out the dissolution stage of Electrochemical Detection, conversion circuit exports electric current to working electrode, reference electrode inputs variation voltage to difference amplifier, the microcontroller can be analyzed and processed the voltage of the variation and the function of time, the microcontroller is calculated according to Nernst equation into the value to content of beary metal, when being detected again, conversion circuit first exports constant voltage to auxiliary electrode, make on the intracorporal heavy metal accumulation to electrode of water, microcontroller control conversion circuit exports electric current to working electrode after the completion of enrichment, reference electrode inputs variation voltage to difference amplifier, microcontroller, which can be analyzed and processed the voltage of variation and the function of time, reaches a huge sum of money in measurement water body Belong to the purpose of content, such method has the characteristics that the amount of dissolution is high compared to traditional stripping voltammetry, so that precision of the invention is higher.
Description
Technical field
The present invention relates to heavy metal analysis field, in particular to a kind of heavy metal detector and its electrolytic cell.
Background technique
Heavy metal pollution have become influence human body health key factor, the heavy metals such as lead, cadmium, mercury, arsenic, be due to
The development of industrial activity causes the enrichment in mankind's ambient enviroment, enters human body by big gas and water, food etc., in human body
Accumulation in a little organs, causes slow poisoning, is detrimental to health.Heavy metal detector in the prior art mostly uses greatly dissolution to lie prostrate
Peace method (also known as reversed stripping polarography), this method is to make tested substance, is generating limit electricity to measured ion polarographic analysis
It is electrolysed the regular hour under the current potential of stream, then changes the current potential of electrode, dissolves out the substance being enriched on this electrode again, root
Quantitative analysis is carried out according to volt-ampere curve obtained in process in leaching.
Application No. is the Chinese patents of CN201510987925.4, including electrolytic cell, mixing control device, microcontroller, work
Make electrode, reference electrode, auxiliary electrode, potentiostat and microcontroller；The detection port connection working electrode of potentiostat,
Reference electrode, auxiliary electrode；Microcontroller converts voltage signal for digital signal by D/A converter and controls potentiostat work
Make, potentiostat converts digital signal for voltage signal by A/D converter and is sent in microcontroller；Microcontroller with it is micro-
Controller connection.Heavy metal concentration in solution is measured by stripping voltammetry, and converts it into voltage signal；A/D converter
Microcontroller is sent to after voltage signal is converted to digital signal；It realizes long-range monitoring, reaches to water sample heavy metal analysis
Purpose.But such heavy metal detector can not make all electrodes that are enriched in when adding backward voltage to carry out heavy metal dissolution
Heavy metal achievees the effect that dissolve out completely, reduces detection accuracy.
Summary of the invention
It is an object of the present invention to provide a kind of heavy metal analysis electrolytic cells, can be improved the essence of heavy metal analysis
Degree.
Above-mentioned purpose of the invention has the technical scheme that
A kind of heavy metal analysis electrolytic cell, including microcontroller, constant potential generator, difference amplifier, auxiliary electrode, reference
Electrode, working electrode and conversion circuit, the microcontroller convert voltage signal control for digital signal by D/A converter
Constant potential generator work, the difference amplifier voltage signal is converted to after digital signal by A/D converter be sent to it is micro-
Controller, when carrying out the concentration stage of Electrochemical Detection, conversion circuit exports constant voltage to auxiliary electrode, is carrying out electrification
When learning the dissolution stage of detection, conversion circuit exports electric current to working electrode, and reference electrode changes to difference amplifier input one
Voltage, the variation voltage and time form a function, by Nernst equation can deduce the function there are several areas of permanent pressure,
The time span of the areas of permanent pressure is directly proportional to the content of metal dissolved out when being located at this constant pressure, and the microcontroller can root
The content height of such metal is judged according to the time for the metal dissolving for being located at this areas of permanent pressure.
By using above-mentioned technical proposal, when being detected, conversion circuit first exports constant voltage to auxiliary electrode, makes
On the intracorporal heavy metal accumulation to electrode of water, microcontroller control conversion circuit exports electric current to working electrode after the completion of enrichment,
Reference electrode forms a function, You Nengsi special formula with the time to one variation voltage of difference amplifier input, the variation voltage
Journey can deduce the function, and there are several areas of permanent pressure, the time span of the areas of permanent pressure and the gold dissolved out when being located at this constant pressure
The content of category is directly proportional, and the microcontroller can judge containing for such metal according to the time for the metal dissolving for being located at this areas of permanent pressure
Amount height, such method has the characteristics that the amount of dissolution is high compared to traditional stripping voltammetry, so that precision of the invention is higher.
The present invention can be further arranged to, and the conversion circuit includes the first gating module, the second gating module and third
Gating module can export constant voltage to auxiliary electrode in concentration stage, can be defeated to working electrode at the stage of dissolution
Constant current out is exported by reference electrode.
By using above-mentioned technical proposal, pass through matching for the first gating module, the second gating module and third gating module
It closes, reaches constant potential generator and realize by being transformed into auxiliary electrode output constant voltage to working electrode output electric current, while
The purpose that reference electrode is exported again while to working electrode output constant current.
The present invention can be further arranged to, the conversion circuit include the first Voltage stabilizing module, first Voltage stabilizing module with
The auxiliary electrode coupling.
By using above-mentioned technical proposal, the first Voltage stabilizing module can play the role of pressure stabilizing, and then mention to auxiliary electrode
For stable voltage.
The present invention can be further arranged to, first Voltage stabilizing module include the first pressure stabilizing operational amplifier, described first
The positive external power supply end of pressure stabilizing operational amplifier and negative external power supply end difference the first filter capacitor in parallel and the second filter capacitor.
By using above-mentioned technical proposal, the first pressure stabilizing operational amplifier plays the role of pressure stabilizing, the first filter capacitor and
Second filter capacitor plays the role of filtering, provides stable voltage for auxiliary electrode and reaches raising heavy metal analysis electrolytic cell essence
The purpose of degree.
The present invention can be further arranged to, and the conversion circuit includes protective module, the protective module respectively with it is described
Reference electrode, working electrode and auxiliary electrode coupling.
By using above-mentioned technical proposal, when heavy metal analysis electrolytic cell does not sample water body, protective module plays guarantor
Protect the purpose of reference electrode, working electrode and auxiliary electrode.
The present invention can be further arranged to, and the protective module includes the first protective resistance and the second protective resistance, described
First protective resistance is coupled with the reference electrode working electrode respectively, the section of first protective resistance and the reference electrode
Point couples second protective resistance, and second protective resistance and the auxiliary electrode couple.
By using above-mentioned technical proposal, the first protective resistance is coupled with the reference electrode working electrode respectively, can be
Access, reference electrode and auxiliary electrode are formed between reference electrode and working electrode, and access, work are formed by the second protective resistance
Make to form access by the first protective resistance and the second protective resistance between electrode and auxiliary electrode, and then reaches to reference electricity
The purpose that pole, working electrode and auxiliary electrode are protected.
The present invention can be further arranged to, and first protective resistance and the second protective resistance are variable resistance.
By using above-mentioned technical proposal, by the resistance value point for adjusting the first protective resistance and the second protective resistance
The size for not adjusting its partial pressure, plays the role of protection to reference electrode, working electrode and auxiliary electrode respectively.
The present invention can be further arranged to, and the conversion circuit includes the second Voltage stabilizing module, second Voltage stabilizing module
Input terminal and the reference electrode couple, and the output end and the difference amplifier of second Voltage stabilizing module couple.
By using above-mentioned technical proposal, the second Voltage stabilizing module can play the role of pressure stabilizing, and then to difference amplifier
Export stable voltage.
The present invention can be further arranged to, second Voltage stabilizing module include the second pressure stabilizing operational amplifier, described second
The positive external power supply end of pressure stabilizing operational amplifier and negative external power supply end difference third filter capacitor in parallel and the 4th filter capacitor.
By using above-mentioned technical proposal, the second pressure stabilizing operational amplifier plays the role of pressure stabilizing, third filter capacitor and
4th filter capacitor plays the role of filtering, provides stable voltage for auxiliary electrode and reaches raising heavy metal analysis electrolytic cell essence
The purpose of degree.
It is another object of the present invention to provide a kind of heavy metal detector, it can be achieved that sampling water body be sampled,
Resolution and the purpose detected by heavy metal analysis electrolytic cell.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of heavy metal detector further includes having digestion device, devil liquor recovery dress including above-mentioned heavy metal analysis electrolytic cell
Set and water circulation system, the water circulation system can control sampling water body, make its after digestion device is cleared up extremely
The heavy metal analysis electrolytic cell is detected.
And then achieve the purpose that detect heavy metal in water, water circulation system can drain into sampling water body described useless after detection
Liquid recyclable device can control sampling water body by water circulation system, clear up it by digestion device, pass through after resolution
It crosses to electrolytic cell and carries out the measurement of heavy metal concentration, waste liquid recovery apparatus is emitted into after being measured and carries out devil liquor recovery, is carried out
Processing.
In conclusion the invention has the following advantages:
Conversion circuit first exports constant voltage to auxiliary electrode, makes to be enriched on the intracorporal heavy metal accumulation to electrode of water
Electric current is exported to working electrode at rear microcontroller control conversion circuit, reference electrode inputs variation voltage to difference amplifier,
The variation voltage and time formation function, can deducing the function by Nernst equation, there are several areas of permanent pressure, the perseverances
The time span of pressure area is directly proportional to the content of metal that is dissolved out when being located at this constant pressure, and the microcontroller can be according to being located at
The time of the metal dissolving of this areas of permanent pressure judges the content height of such metal, and such method is compared to traditional stripping voltammetry
Have the characteristics that the amount of dissolution is high, so that precision of the invention is higher, conversion circuit includes the first Voltage stabilizing module, first pressure stabilizing
Module and the auxiliary electrode couple, and the first Voltage stabilizing module can play the role of pressure stabilizing, and then provide stabilization to auxiliary electrode
Voltage, conversion circuit includes the second Voltage stabilizing module, and the input terminal of second Voltage stabilizing module and the reference electrode couple, institute
The output end and the difference amplifier for stating the second Voltage stabilizing module couple, and the second Voltage stabilizing module can play the role of pressure stabilizing, into
And stable voltage is exported to difference amplifier.
Detailed description of the invention
Fig. 1 is one schematic diagram of embodiment；
Fig. 2 is conversion circuit schematic diagram；
Fig. 3 is the function schematic diagram of voltage and time；
Fig. 4 is the first circuit diagram of conversion circuit；
Fig. 5 is the second servo loop schematic diagram of conversion circuit；
Fig. 6 is two schematic diagram of embodiment.
In figure, the 110, first gating module；120, the second gating module；130, third gating module；140, the first pressure stabilizing
Module；150, the second Voltage stabilizing module；160, protective module；170, unsteady flow module.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
Embodiment one: a kind of heavy metal analysis electrolytic cell, as shown in Figure 1, including microcontroller, constant potential generator, difference
Amplifier, auxiliary electrode, reference electrode, working electrode and conversion circuit, the microcontroller are believed number by D/A converter
It number is converted into voltage signal control constant potential generator work, constant potential generator provides voltage for conversion circuit, and conversion circuit is to work
Make electrode, auxiliary electrode and reference electrode and voltage or electric current are provided, and output voltage signal to follower of checking the mark, the difference is put
Voltage signal is converted to after digital signal by big device by A/D converter is sent to microcontroller, and then completes to sampling water body
The measurement of middle content of beary metal.
Conversion circuit schematic diagram shown in Fig. 2, the first gating module 110, including the first single-pole double-throw switch (SPDT) S1, described first
First plug-in strip S1 of single-pole double-throw switch (SPDT) and the constant potential generator couple, the first contact of first single-pole double-throw switch (SPDT) with
The auxiliary electrode coupling, the second contact of first single-pole double-throw switch (SPDT) and the working electrode couple, the second gating mould
Block 120, including the second single-pole double-throw switch (SPDT), the second plug-in strip S2 and the difference amplifier of the second single-pole double-throw switch (SPDT) are coupled,
The third contact of second single-pole double-throw switch (SPDT) and the working electrode couple, third gating module 130, including third hilted broadsword
Commutator, the third plug-in strip S3 and the reference electrode of third single-pole double-throw switch (SPDT) are coupled, the third single-pole double-throw switch (SPDT)
The 5th contact and the auxiliary electrode module couples, the 6th contact of the third single-pole double-throw switch (SPDT) and second hilted broadsword
4th contact of commutator couples.
Conversion circuit includes the first Voltage stabilizing module 140, and first Voltage stabilizing module 140 is coupled with the auxiliary electrode, institute
State the first Voltage stabilizing module 140 include the first pressure stabilizing operational amplifier AD795JR, the first pressure stabilizing operational amplifier it is just external
The first filter capacitor C1 of parallel connection and the second filter capacitor C2, the first pressure stabilizing operation are put respectively for power end and negative external power supply end
The model AD795JR of big device.
The conversion circuit includes protective module 160, and the protective module 160 is electric with the reference electrode, work respectively
Pole and auxiliary electrode coupling, the protective module 160 include the first protective resistance R4 and the second protective resistance R3, and described first protects
It protects resistance R4 to couple with the reference electrode working electrode respectively, the node of the first protective resistance R4 and the reference electrode
The second protective resistance R3 is coupled, the second protective resistance R3 and the auxiliary electrode couple, first protective resistance
R4 and the second protective resistance R3 is variable resistance, and the first protective resistance R4 is coupled with the reference electrode working electrode respectively, can
Formed between reference electrode and working electrode access, reference electrode and auxiliary electrode formed by the second protective resistance R3 it is logical
Road forms access by the first protective resistance R4 and the second protective resistance R3 between working electrode and auxiliary electrode, and then reaches
To the purpose of reference electrode, working electrode and auxiliary electrode protection.
Conversion circuit includes the second Voltage stabilizing module 150, the input terminal and the reference electrode of second Voltage stabilizing module 150
Coupling, the output end and the difference amplifier of second Voltage stabilizing module 150 couple, and the second Voltage stabilizing module 150 can play
The effect of pressure stabilizing, and then stable voltage is exported to difference amplifier, second Voltage stabilizing module 150 includes the second pressure stabilizing operation
Amplifier, the positive external power supply end of the second pressure stabilizing operational amplifier and negative external power supply end difference third filter capacitor in parallel
C5 and the 4th filter capacitor C4, the second pressure stabilizing operational amplifier play the role of pressure stabilizing, the filtering of third filter capacitor C5 and the 4th
Capacitor C4 plays the role of filtering, provides the mesh that stable voltage reaches raising heavy metal analysis electrolytic cell precision for auxiliary electrode
, the model AD795JR of the second pressure stabilizing operational amplifier.
The conversion circuit further includes unsteady flow module 170, and the unsteady flow module 170 is coupled with the working electrode, described
Unsteady flow module 170 includes electric capacity of voltage regulation C6 and variable resistance R5, to working electrode and then the adjusting to variable resistance R5
Electric current is adjusted, and adjusts current value when achieving the purpose that add working electrode reverse current.
Linear function figure as shown in Figure 3, abscissa are time t, and ordinate is voltage U, variation voltage U and time t shape
At a function, by Nernst equation can deduce the function there are several areas of permanent pressure, the time span of the areas of permanent pressure be located at
The content of the metal dissolved out when this constant pressure is directly proportional, the first voltage value corresponding to areas of permanent pressure 1 as shown in the figure, this first voltage
Value is the dissolution voltage of substance A, and time t1 is then the dissolution time of substance A, second voltage value corresponding to areas of permanent pressure 2, this
Two voltage values are the dissolution voltage of substance B, and time t2 is then the dissolution time of substance B, tertiary voltage corresponding to areas of permanent pressure 3
Value, this third voltage value is the dissolution voltage of substance C, and time t3 is then the dissolution time of substance C, and the microcontroller can root
The content height of such metal is judged according to the time for the metal dissolving for being located at areas of permanent pressure.
Fig. 4 is the first circuit diagram of conversion circuit, and the first plug-in strip S1 passes through 140 pieces of the first pressure stabilizing mould and auxiliary electrode
Coupling, the reference electrode is by the second Voltage stabilizing module 150 by the reversed input of the second plug-in strip S2 and the first Voltage stabilizing module 140
End coupling, the working electrode are exported with third plug-in strip S3 coupling.
Fig. 5 is the second servo loop schematic diagram of conversion circuit, and working electrode is coupled by unsteady flow module 170 and the first plug-in strip
S1, reference electrode are exported by the second Voltage stabilizing module 150, third plug-in strip S3 and the second plug-in strip S2.
Embodiment two: a kind of heavy metal detector, the electrolytic cell including embodiment one, as shown in fig. 6, further including having resolution
Device, waste liquid recovery apparatus and water circulation system, the water circulation system can control sampling water body, make it by digestion device
It is detected after being cleared up to the heavy metal analysis electrolytic cell, and then achievees the purpose that detect heavy metal in water, inspection
Sampling water body can be drained into the waste liquid recovery apparatus by water circulation system after survey, and water circulation system can control sampling water body
System clears up it by digestion device, by carrying out the measurement of heavy metal concentration to electrolytic cell after resolution, is measured heel row
It puts to waste liquid recovery apparatus and carries out devil liquor recovery, handled.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (9)
1. a kind of heavy metal analysis electrolytic cell, including microcontroller, constant potential generator, difference amplifier, auxiliary electrode, reference electricity
Pole, working electrode and conversion circuit, the microcontroller convert voltage signal control perseverance for digital signal by D/A converter
Generator work is pressed, the difference amplifier is sent to micro-control after voltage signal is converted to digital signal by A/D converter
Device processed, it is characterized in that: conversion circuit exports constant voltage to auxiliary electrode when carrying out the concentration stage of Electrochemical Detection,
When carrying out the dissolution stage of Electrochemical Detection, conversion circuit exports electric current to working electrode, and reference electrode is defeated to difference amplifier
Enter a variation voltage, the variation voltage and time form a function, if can deduce that the function exists by Nernst equation
Dry areas of permanent pressure, the time span of the areas of permanent pressure is directly proportional to the content of metal dissolved out when being located at this constant pressure, described micro-
Controller can judge the content height of such metal according to the time for the metal dissolving for being located at this areas of permanent pressure;
The conversion circuit includes the first gating module (110), the second gating module (120) and third gating module (130), energy
It is enough that constant voltage is exported to auxiliary electrode in concentration stage, it can be to working electrode output constant current, by joining at the stage of dissolution
It is exported than electrode.
2. a kind of heavy metal analysis electrolytic cell according to claim 1, it is characterized in that: the conversion circuit includes first steady
Die block (140), first Voltage stabilizing module (140) and the auxiliary electrode couple.
3. a kind of heavy metal analysis electrolytic cell according to claim 2, it is characterized in that: first Voltage stabilizing module (140)
Including the first pressure stabilizing operational amplifier, the positive external power supply end of the first pressure stabilizing operational amplifier and negative external power supply end difference
First filter capacitor and the second filter capacitor in parallel.
4. a kind of heavy metal analysis electrolytic cell according to claim 1, it is characterized in that: the conversion circuit includes protection mould
Block (160), the protective module (160) couple with the reference electrode, working electrode and auxiliary electrode respectively.
5. a kind of heavy metal analysis electrolytic cell according to claim 4, it is characterized in that: the protective module (160) includes
First protective resistance and the second protective resistance, first protective resistance are coupled with the reference electrode working electrode respectively, institute
The node for stating the first protective resistance and the reference electrode couples second protective resistance, second protective resistance with it is described
Auxiliary electrode coupling.
6. a kind of heavy metal analysis electrolytic cell according to claim 5, it is characterized in that: first protective resistance and second
Protective resistance is variable resistance.
7. a kind of heavy metal analysis electrolytic cell according to claim 1, it is characterized in that: the conversion circuit includes second steady
Die block (150), the input terminal and the reference electrode of second Voltage stabilizing module (150) couple, second Voltage stabilizing module
(150) output end and the difference amplifier couples.
8. a kind of heavy metal analysis electrolytic cell according to claim 7, it is characterized in that: second Voltage stabilizing module (150)
Including the second pressure stabilizing operational amplifier, the positive external power supply end of the second pressure stabilizing operational amplifier and negative external power supply end difference
Third filter capacitor and the 4th filter capacitor in parallel.
9. a kind of heavy metal detector, it is characterized in that: including the heavy metal species inspection as described in any one of claim 1-8
Electrolytic cell is surveyed, further includes having digestion device and water circulation system, the water circulation system can control sampling water body, make its warp
It crosses after digestion device is cleared up and carries out the detection of content of beary metal to the heavy metal analysis electrolytic cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252388.3A CN107305194B (en) | 2016-04-21 | 2016-04-21 | A kind of heavy metal detector and its electrolytic cell |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610252388.3A CN107305194B (en) | 2016-04-21 | 2016-04-21 | A kind of heavy metal detector and its electrolytic cell |
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| CN107305194A CN107305194A (en) | 2017-10-31 |
| CN107305194B true CN107305194B (en) | 2019-06-25 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957592A (en) * | 1974-07-29 | 1976-05-18 | Owens-Illinois, Inc. | Measurement of polarographic current |
| CN1595136A (en) * | 2004-06-18 | 2005-03-16 | 刘文涛 | Anodic stripping voltammetry |
| CN102608191A (en) * | 2011-12-08 | 2012-07-25 | 青岛佳明测控仪器有限公司 | Electrochemistry on-line cleaning method for heavy metal on-line monitor working electrode |
| CN102928496A (en) * | 2011-08-11 | 2013-02-13 | 江苏天瑞仪器股份有限公司 | Portable water heavy metal analyzer and analytic method thereof |
| CN105388204A (en) * | 2015-12-22 | 2016-03-09 | 天津格信智能科技有限公司 | Heavy metal detection system adopting novel stripping voltammetry |
-
2016
- 2016-04-21 CN CN201610252388.3A patent/CN107305194B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957592A (en) * | 1974-07-29 | 1976-05-18 | Owens-Illinois, Inc. | Measurement of polarographic current |
| CN1595136A (en) * | 2004-06-18 | 2005-03-16 | 刘文涛 | Anodic stripping voltammetry |
| CN102928496A (en) * | 2011-08-11 | 2013-02-13 | 江苏天瑞仪器股份有限公司 | Portable water heavy metal analyzer and analytic method thereof |
| CN102608191A (en) * | 2011-12-08 | 2012-07-25 | 青岛佳明测控仪器有限公司 | Electrochemistry on-line cleaning method for heavy metal on-line monitor working electrode |
| CN105388204A (en) * | 2015-12-22 | 2016-03-09 | 天津格信智能科技有限公司 | Heavy metal detection system adopting novel stripping voltammetry |
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