CN101498681B - Electrode for measuring trace dissolved oxygen - Google Patents
Electrode for measuring trace dissolved oxygen Download PDFInfo
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- CN101498681B CN101498681B CN2009100475777A CN200910047577A CN101498681B CN 101498681 B CN101498681 B CN 101498681B CN 2009100475777 A CN2009100475777 A CN 2009100475777A CN 200910047577 A CN200910047577 A CN 200910047577A CN 101498681 B CN101498681 B CN 101498681B
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Abstract
An electrode for measuring micro dissolved oxygen belongs to the technical field of electrochemical sensors. On the basis of the original battery type electrodes, the electrode adopts a spongy-shaped lead as the positive electrode so as to greatly increase the effective area of the positive electrode and enable the surface and the interior of the positive electrode to both react with oxygen molecules of the dissolved oxygen, thereby greatly prolonging the service life of the electrode, increasing the sensitivity of the electrode to the oxygen molecules and outputting large and stable signals under the condition of measuring the micro dissolved oxygen; with output current being three magnitudes larger than a traditional electrode, the electrode has the advantages of high capacity of resisting disturbance, stable performance, good reproducibility, convenient use, less electrode maintenance, and the like, and is particularly suitable for measuring or on line monitoring the micro dissolved oxygen in water fed to a boiler in a heat power station or nuclear power station.
Description
Technical field
The present invention relates to a kind of electrode of measuring trace dissolved oxygen, belong to the technical field of electrochemical sensor.
Background technology
Analyzing the boiler feedwater of generating plant and the content of the dissolved oxygen DO in the condensate all is trace level, and the former is at several μ g/L, and the latter is in the scope of≤30 μ g/L.This is to prevent boiler and the condensing engine necessary condition that work is not corroded under high temperature, high pressure.Above-mentioned water need be introduced into the deaeration plant deoxygenation before getting into boiler and condensing engine, and the amount of the deoxygenation chemicals of in deaeration plant, throwing in needs to be monitored by dissolved oxygen analytic instrument.Dissolved oxygen analytic instrument is the indispensable instrument in generating plant.
The electrode of the measurement trace dissolved oxygen that present dissolved oxygen analytic instrument both domestic and external is used all develops from the constant dissolved oxygen electrode and comes, and in fact is exactly the constant dissolved oxygen electrode, mainly contains two kinds.The work of first kind of electrode applies a polarizing voltage based on polarogram formula principle on electrode.When dissolved oxygen DO during at the electrode internal reaction, this electrode can produce a concentration dependent electric current with dissolved oxygen DO, promptly exports signal.The weak point of polarogram formula electrode is: 1, for measuring trace dissolved oxygen, the sensitivity of electrode is low, and the output signal is little; 2, the electrode useful area of electrode is little, is prone to account for dirt; 3, in the use, fill the electrolytic solution easy consumption in the electrode, replenish, and the installation ten minutes difficulty of replenishing rear electrode.The work of second kind of electrode is based on primary element formula principle, and the anode of this electrode is plumbous, and when this electrode measurement dissolved oxygen DO, this electrode can produce a concentration dependent electric current with dissolved oxygen DO, promptly exports signal.The oxygen molecule of lead anode and dissolved oxygen DO reaction simultaneously generates brown lead oxide, covers the surface of lead electrode, and electrode performance is descended gradually, and even loses efficacy.The shortcoming of galvanic cell formula electrode is: 1, the surface area of lead electrode is little, and the surface of lead electrode can be covered by brown lead oxide fully soon, and promptly the working life of this electrode is short; 2, the sensitivity of electrode is low, and the output signal is little.
Summary of the invention
The technical matters that the present invention will solve is to release a kind of electrode of measuring trace dissolved oxygen, not only this electrode shortcoming of existing electrode, also has sensitively, and the output signal is big, the advantage of reliable and stable and favorable reproducibility.
For achieving the above object, the present invention adopts following technical scheme.This electrode is characterised in that, on the basis of existing primary element formula electrode, adopts spongy lead as anode; Increased the useful area of anode widely; The surface of anode can both be reacted with the oxygen molecule of dissolved oxygen DO with inner, greatly prolonged the serviceable life of electrode, and increased the susceptibility of electrode pair oxygen molecule; Under the condition of measuring trace dissolved oxygen, the output signal is stablized greatly.
Be described with reference to the accompanying drawings technical scheme of the present invention at present.A kind of electrode of measuring trace dissolved oxygen contains cable tube joint 1, cable seal O shape rubber band 2, arc-spark stand 16, lead anode 9, silver cathode 8, electrolytic solution 10, macromolecule membrane 7, lock ring O shape rubber band 6, cylinder ring 12, electrolytic solution sealing O shape rubber band 110, fastening bolt 11, and cable tube joint 1 is the hollow nut of being processed by the PE material, is shaped on first screw thread 25 on the hitching post of this nut; Central part office at the cap of this nut has first cable aperture 24, and arc-spark stand 16 contains electrode fairlead 160 and electrode fixed mount 161, and electrode fairlead 160 is pipes of being processed by the PE material, is shaped on the 3rd screw thread 165 and the 4th screw thread 164 on the inwall at the two ends of this pipe respectively; Have the inside with this pipe to be divided into two-part circular shim in this pipe, have at the core of this shim and connect described two-part second cable aperture 23, be shaped on measuring cell connector 3 on the outer wall of this pipe, this connector contains flange 30, watertight O shape rubber band 31 and second screw thread 32; Watertight O shape rubber band 31 hoops are enclosed within on the outer wall of the electrode fairlead 160 between the flange 30 and second screw thread 32, and the parting face was that stepped appearance De rotation is turned during electrode fixed mount 161 was processed, indulged by the PE material, and an end of this fixed mount has a class, and the bus De rotation of this class changes the bus De rotation commentaries on classics radius of radius less than this fixed mount; On the cylinder that the De of this class rotation is turned, be shaped on the 5th screw thread 163, on the De of this class rotation is turned, be shaped on central shaft and the De of this class rotation cylindrical pitting that rotating shaft 0 overlaps of turning, the other end of this fixed mount has two classes, and the bus De rotation of first class changes radius and changes radius less than the bus De rotation of this fixed mount; The bus De rotation that on the cylinder that the De of this class rotation is turned, is shaped on the 6th screw thread 162, the second classes changes radius and changes radius less than the bus De rotation of first class, on the outer wall of this fixed mount, is shaped on the circular groove that twice are parallel to each other, and on this fixed mount, has the straight circular hole of bottom surface of end face and the described cylindrical pitting of the other end that runs through this fixed mount; The central shaft of this straight circular hole overlaps with the rotating shaft of this fixed mount 0, on this fixed mount, has oblique circular hole 166, and this oblique circular hole runs through annular plane and the bottom surface of described cylindrical pitting between the cylinder that the radius Jiao Da De rotation of the other end of the cylinder that is clipped in this fixed mount and this fixed mount turns; Lead anode 9 is poles of being processed by lead, and silver cathode 8 is silver pipes, and the inwall at the two ends of this pipe is shaped on the 7th screw thread 82 and the 8th screw thread 81 respectively; Have many apertures that are uniformly distributed with 80 on the tube wall of this pipe, the ratio of the area summation of aperture 80 and silver electrode 8 outer wall areas is between 1: 50～70, macromolecule membrane 7 be columnar, do not seep water but can see through the organic film of oxygen; Cylinder ring 12 is pipes of being processed by the PE material, and the external diameter of an end of this pipe is less, on the tube wall of said end, is shaped on the 9th screw thread 121; On the inwall of this pipe, be shaped on the tenth screw thread 120, on the outer wall of this pipe, be shaped on the circular groove that twice are parallel to each other, fastening bolt 11 is bolts of being processed by the PE material; Be shaped on the 11 screw thread 111 on the hitching post of this bolt, lead anode 9 to be inserting above-mentioned straight circular hole with the above-mentioned friction tight mode of straight circular hole, and stretch out from the end face of the other end of the bottom surface of described cylindrical pitting and electrode fixed mount 161 respectively at the two ends of lead anode 9; Filamentary silver 22 twines a circle on the 6th screw thread 162, silver cathode 8 is screwed onto with electrode fixed mount 161 through the 7th screw thread 82 and the 6th screw thread 162, and filamentary silver 22 is clipped between silver cathode 8 and the electrode fixed mount 161; Pass oblique circular hole 166 after two terminations of filamentary silver 22 are stranded and stretch out from the bottom surface of described cylindrical pitting, the external diameter of silver cathode 8 equates that with the external diameter of electrode fixed mount 161 termination and the lead anode 9 of first heart yearn 18 of cable 20 are welded into anode soldering tip 4; The termination and the filamentary silver 22 of second heart yearn 17 of cable 20 are welded into negative electrode soldering tip 21, and electrode fairlead 160 is spirally connected into arc-spark stand 16 through the 4th screw thread 164 with the 5th screw thread 163 with electrode fixed mount 161 passes second cable aperture 23 with cable 20 mode, and cable tube joint 1 passes the O shape hole of cable seal O shape rubber band 2 with electrode fairlead 160 with cable 20 and the mode of second cable aperture 24 is screwed onto together through first screw thread 25 and the 3rd screw thread 165; Cylinder ring 12 is screwed onto together through the 8th screw thread 81 and the 9th screw thread 121 with electrode fixed mount 161, and the external diameter of cylinder ring 12 equates with the external diameter of electrode fixed mount 161, covers the macromolecule membrane 7 that is covered with the pipe shape on the outer wall of silver cathode 8; Each is close to the two ends of macromolecule membrane 7 it on circular groove that circular groove that twice on electrode fixed mount 161 are parallel to each other and the twice on the cylinder ring 12 are parallel to each other respectively with twice lock ring O shape rubber band 6, and filling is with electrolytic solution 10 in the space between lead anode 9 and silver cathode 8, and fastening bolt 11 seals O shape rubber band 110, the tenth screw thread 120 and the 11 screw thread 111 through electrolytic solution and is screwed onto with cylinder ring 12 with the mode that electrolytic solution 10 does not leak outside; It is characterized in that an end of the lead anode 9 that stretches out at the end face from the described other end of electrode fixed mount 161 is fixed with spongy lead cylinder 15, the central shaft of this cylinder overlaps with the central shaft of lead anode 9.Spongy lead cylinder 15 is formed by the sub-coalescence of small lead button, and the space is arranged between particle, and spongy lead cylinder 15 is equivalent to the very large plumbous surface of area, and in other words, spongy lead cylinder 15 has increased the surface area of lead anode 9.When the trace dissolved oxygen in the electrode measurement of the present invention water sample to be measured, the plumbous surface of the part of spongy lead cylinder 15 can be changed PbO into
2, the surface of this part will lose the activity of measuring dissolved oxygen, and the big plumbous surface of spongy lead cylinder 15 guarantees that electrode of the present invention has long service life.
Technical scheme of the present invention is further characterized in that, in described cylindrical pitting, is perfused with anode soldering tip 4 and negative electrode soldering tip 21 are locked in the epoxy resin 5 in the described cylindrical pitting.The effect of epoxy resin 5 is to make anode soldering tip 4 and negative electrode soldering tip 21 isolated with electrolytic solution 10, does not allow the slit of electrolytic solution 10 between oblique circular hole 166 and lead anode 9 and electrode fixed mount 161 and oozes out.
Technical scheme of the present invention is further characterized in that, epoxy resin 5 top has flowable state silicon rubber 50 and cure silicone rubber 51 successively.Flowable state silicon rubber 50 makes anode soldering tip 4 isolated with negative electrode soldering tip 21 and air.Because if anode soldering tip 4 contacts with air with negative electrode soldering tip 21, two soldering tips and air are formed primary element, record airborne oxygen content, can cause error to the measured value of final trace dissolved oxygen.Only seal anode soldering tip 4 and negative electrode soldering tip 21 not enough with epoxy resin 5, because the slit can be left in the junction of two kinds of different materials of epoxy resin 5 and two soldering tips, and flowable state silicon rubber 50 can be sealed these slits, stops contacting of two soldering tips and air fully.The effect of cure silicone rubber 51 is to seal flowable state silicon rubber 50, does not allow it to leak outside.
Technical scheme of the present invention is further characterized in that electrolytic solution 10 is that concentration is the soda mint of 8wt%～10wt%.When the trace dissolved oxygen in the electrode measurement of the present invention water sample to be measured, the dissolved oxygen DO in the water sample to be measured carries out following redox reaction through aperture is after 80s in the primary element of being made up of silver cathode 8, lead anode 9 and spongy lead cylinder 15 thereof and electrolytic solution 10:
On the negative electrode: O
2+ 2H
2O+4e → 4 (OH)
-
On the anode: 2Pb+4 (OH)
--4e → 2Pb (OH)
2
Technical scheme of the present invention is further characterized in that; The external diameter of spongy lead cylinder 15 equates with the external diameter of the end face of the described other end of electrode fixed mount 161; On the cylinder of the outer wall of spongy lead cylinder 15 and the cylinder that contains said end face, cover and be covered with anode sheath 14, anode sheath 14 is the porous polymer materials that can pass through oxygen and electrolytic solution 10.The purpose of doing like this is to stop possibility that the spongy lead cylinder 15 on the lead anode 9 contacts with silver cathode 8, prevent that lead button from peeling off and keep the unimpeded of oxygen and electrolyte 10 from spongy lead cylinder 15.
Compare advantage of the present invention with background technology:
1, metering circuit is simple
The electrode of background technology can not produce and the dissolved oxygen concentration output signal related, and must add a polarizing voltage could produce.Electrode of the present invention can produce and the dissolved oxygen concentration output signal related.Two kinds of electrodes in use, the former metering circuit is complicated, the latter's metering circuit is simple.
2, do not align the trouble of polarizing voltage platform
The electrode of background technology is along with its polarizing voltage platform of time can move to right and diminish.This electrode in use, the user will constantly align its polarizing voltage platform, and is cumbersome.This use inconvenience will be extended to till this electrode failure, the polarizing voltage abolition of plateau always.Electrode of the present invention does not have the polarizing voltage platform, this electrode in use, basic trouble of just not aligning the polarizing voltage platform.
3, the output signal is big, strong interference immunity
When the electrode of use background technology and electrode measurement concentration of the present invention were the dissolved oxygen DO of 5 μ g/L, the former output signal was 0.4nA, and the latter's output signal is 0.2 μ A, than the former big three one magnitude, strong interference immunity.
4, the maintenance of electrode is few
The electrode of background technology in use, the electrolytic solution in it can be consumed, every mistake will be upgraded once electrolytic liquid in one, two months, the maintenance of electrode is complicated, and is time-consuming, and very easyly when changing electrolytic solution causes breathable films to break.Electrode of the present invention in use, the electrolytic solution in it does not consume, the maintenance of electrode is few.
5, the anode useful area is big, and contamination resistance is strong, long service life
The anode useful area of the electrode of background technology is little, usually 1.5cm only
2About, contamination resistance is poor, and serviceable life is short.Electrodes use spongy lead cylinder 15 of the present invention is as the extension of lead anode 9, and the summation of forming each small lead button area of mossy lead cylinder 15 is its useful area, and the useful area of anode is big, and contamination resistance is strong, long service life.
6, need not change macromolecule membrane, the electrode use cost is cheap
The electrode of background technology in use, every mistake will be changed electrolytic solution in one, two months again, needed related replacing macromolecule membrane, the electrode use cost is high.Electrode of the present invention in use need not changed macromolecule membrane, and the electrode use cost is cheap.
Description of drawings
Fig. 1 is the structural representation of electrode of the present invention, this figure middle part have one section key structure of showing electrode in cut open structural representation.Cut open structural representation in Fig. 2 electrode of the present invention.In Fig. 1 and Fig. 2, the 0th, the rotating shaft of electrode fixed mount 161 overlaps with the central shaft of electrode of the present invention, and the 1st, cable tube joint, the 2nd, cable seal O shape rubber band, the 3rd, measuring cell connector; The 30th, flange, the 31st, watertight O shape rubber band, 32 is second screw threads, the 4th, anode soldering tip, the 5th, epoxy resin, the 50th, flowable state silicon rubber; The 51st, cure silicone rubber, the 6th, lock ring O shape rubber band, the 7th, macromolecule membrane, the 8th, silver cathode, the 80th, aperture, 81 is the 8th screw threads; 82 is the 7th screw threads, the 9th, and lead anode, the 10th, electrolytic solution, the 11st, the fastening bolt, the 110th, electrolytic solution sealing O shape rubber band, 111 is the 11 screw threads; The 12nd, cylinder ring, 120 is the tenth screw threads, 121 is the 9th screw threads, the 14th, anode sheath, the 15th, spongy lead cylinder, the 16th, arc-spark stand; The 160th, the electrode fairlead, the 161st, the electrode fixed mount, 162 is the 6th screw threads, and 163 is the 5th screw threads, and 164 is the 4th screw threads; 165 the 3rd screw threads, the 166th, oblique circular hole, 17 is second heart yearns, 18 is first heart yearns, the 20th, cable; The 21st, the negative electrode soldering tip, the 22nd, filamentary silver, 23 is second cable aperture, and 24 is first cable aperture, and 25 is first screw threads.
Embodiment
Combine accompanying drawing and embodiment to further specify technical scheme of the present invention at present.The structure of the electrode of the basic structure of the electrode of embodiment 1～4 and measurement trace dissolved oxygen mentioned above is identical, below only enumerates the crucial separately technical data of each embodiment.Embodiment 5 and 6 is that the product to embodiment 4 carries out the conclusion that long-term on-the-spot test test is drawn.
A kind of electrode of measuring trace dissolved oxygen contains cable tube joint 1, cable seal O shape rubber band 2, arc-spark stand 16, lead anode 9, silver cathode 8, electrolytic solution 10, macromolecule membrane 7, lock ring O shape rubber band 6, cylinder ring 12, electrolytic solution sealing O shape rubber band 110, fastening bolt 11, and cable tube joint 1 is the hollow nut of being processed by the PE material, is shaped on first screw thread 25 on the hitching post of this nut; Central part office at the cap of this nut has first cable aperture 24, and arc-spark stand 16 contains electrode fairlead 160 and electrode fixed mount 161, and electrode fairlead 160 is pipes of being processed by the PE material, is shaped on the 3rd screw thread 165 and the 4th screw thread 164 on the inwall at the two ends of this pipe respectively; Have the inside with this pipe to be divided into two-part circular shim in this pipe, have at the core of this shim and connect described two-part second cable aperture 23, be shaped on measuring cell connector 3 on the outer wall of this pipe, this connector contains flange 30, watertight O shape rubber band 31 and second screw thread 32; Watertight O shape rubber band 31 hoops are enclosed within on the outer wall of the electrode fairlead 160 between the flange 30 and second screw thread 32, and the parting face was that stepped appearance De rotation is turned during electrode fixed mount 161 was processed, indulged by the PE material, and an end of this fixed mount has a class, and the bus De rotation of this class changes the bus De rotation commentaries on classics radius of radius less than this fixed mount; On the cylinder that the De of this class rotation is turned, be shaped on the 5th screw thread 163, on the De of this class rotation is turned, be shaped on central shaft and the De of this class rotation cylindrical pitting that rotating shaft 0 overlaps of turning, the other end of this fixed mount has two classes, and the bus De rotation of first class changes radius and changes radius less than the bus De rotation of this fixed mount; The bus De rotation that on the cylinder that the De of this class rotation is turned, is shaped on the 6th screw thread 162, the second classes changes radius and changes radius less than the bus De rotation of first class, on the outer wall of this fixed mount, is shaped on the circular groove that twice are parallel to each other, and on this fixed mount, has the straight circular hole of bottom surface of end face and the described cylindrical pitting of the other end that runs through this fixed mount; The central shaft of this straight circular hole overlaps with the rotating shaft of this fixed mount 0, on this fixed mount, has oblique circular hole 166, and this oblique circular hole runs through annular plane and the bottom surface of described cylindrical pitting between the cylinder that the radius Jiao Da De rotation of the other end of the cylinder that is clipped in this fixed mount and this fixed mount turns, and lead anode 9 is poles of being processed by lead; Silver cathode 8 is silver pipes, and the inwall at the two ends of this pipe is shaped on the 7th screw thread 82 and the 8th screw thread 81 respectively, has many apertures that are uniformly distributed with 80 on the tube wall of this pipe, and the ratio of the area summation of aperture 80 and silver electrode 8 outer wall areas is between 1: 50～70; Macromolecule membrane 7 be columnar, do not seep water but can see through the organic film of oxygen, cylinder ring 12 is pipes of being processed by the PE material, the external diameter of an end of this pipe is less, on the tube wall of said end, is shaped on the 9th screw thread 121; On the inwall of this pipe, be shaped on the tenth screw thread 120, on the outer wall of this pipe, be shaped on the circular groove that twice are parallel to each other, fastening bolt 11 is bolts of being processed by the PE material, is shaped on the 11 screw thread 111 on the hitching post of this bolt; Lead anode 9 to be inserting above-mentioned straight circular hole with the above-mentioned friction tight mode of straight circular hole, and stretch out from the end face of the other end of the bottom surface of described cylindrical pitting and electrode fixed mount 161 respectively at the two ends of lead anode 9, and filamentary silver 22 twines a circle on the 6th screw thread 162, and silver cathode 8 is screwed onto with the 6th screw thread 162 and electrode fixed mount 161 through the 7th screw thread 82; Filamentary silver 22 is clipped between silver cathode 8 and the electrode fixed mount 161, passes oblique circular hole 166 after two terminations of silver 22 are stranded and stretches out from the bottom surface of described cylindrical pitting, and the external diameter of silver cathode 8 equates with the external diameter of electrode fixed mount 161; The termination and the lead anode 9 of first heart yearn 18 of cable 20 are welded into anode soldering tip 4, and the termination and the filamentary silver 22 of second heart yearn 17 of cable 20 are welded into negative electrode soldering tip 21, and electrode fairlead 160 is spirally connected into arc-spark stand 16 through the 4th screw thread 164 with the 5th screw thread 163 with electrode fixed mount 161 passes second cable aperture 23 with cable 20 mode; Cable tube joint 1 passes the O shape hole of cable seal O shape rubber band 2 with electrode fairlead 160 with cable 20 and the mode of second cable aperture 24 is screwed onto together through first screw thread 25 and the 3rd screw thread 165, and cylinder ring 12 is screwed onto together through the 8th screw thread 81 and the 9th screw thread 121 with electrode fixed mount 161, and the external diameter of cylinder ring 12 equates with the external diameter of electrode fixed mount 161; Cover the macromolecule membrane 7 that is covered with the pipe shape on the outer wall of silver cathode 8, each is close to the two ends of macromolecule membrane 7 it on circular groove that circular groove that twice on electrode fixed mount 161 are parallel to each other and the twice on the cylinder ring 12 are parallel to each other respectively with twice lock ring O shape rubber band 6, and filling is with electrolytic solution 10 in the space between lead anode 9 and silver cathode 8; Fastening bolt 11 is screwed onto with cylinder ring 12 with the mode that electrolytic solution 10 does not leak outside through electrolytic solution sealing O shape rubber band 110, the tenth screw thread 120 and the 11 screw thread 111, it is characterized in that, an end of the lead anode 9 that stretches out at the end face from the described other end of electrode fixed mount 161 is fixed with spongy lead cylinder 15; The central shaft of this cylinder overlaps with the central shaft of lead anode 9, in described cylindrical pitting, is perfused with anode soldering tip 4 and negative electrode soldering tip 21 are locked in the epoxy resin 5 in the described cylindrical pitting, and electrolytic solution 10 is that concentration is the soda mint of 8wt%～10wt%; The external diameter of spongy lead cylinder 15 equates with the external diameter of the end face of the described other end of electrode fixed mount 161, on the cylinder of the outer wall of spongy lead cylinder 15 and the cylinder that contains said end face, covers to be covered with anode sheath 14, and anode sheath 14 is the porous polymer materials that can pass through oxygen and electrolytic solution 10.
Embodiment 2
Present embodiment has and identical in structure structure illustrated in figures 1 and 2.Except that also comprising following technical characterictic, remainder is all identical with embodiment 1: epoxy resin 5 top has flowable state silicon rubber 50 and cure silicone rubber 51 successively.
Except that also comprising following gordian technique data, remainder is all identical with embodiment 1:
The diameter of spongy lead cylinder 15 and length are respectively 12mm and 37mm;
The diameter of lead anode 9 and length are respectively 2mm and 45mm, and the one of which end stretches out 3mm from the bottom surface of described cylindrical pitting, and its other end stretches out 32mm from the end face of the other end of described electrode fixed mount 161;
The external diameter of silver cathode 8, wall thickness and length are respectively 16mm, 1.2mm and 43mm;
The diameter of filamentary silver 22 is 0.5mm.
Except that also comprising following gordian technique data, remainder is all identical with embodiment 1:
Epoxy resin 5 top has flowable state silicon rubber 50 and cure silicone rubber 51 successively;
The diameter of spongy lead cylinder 15 and length are respectively 12mm and 37mm;
The diameter of lead anode 9 and length are respectively 2mm and 45mm, and the one of which end stretches out 3mm from the bottom surface of described cylindrical pitting, and its other end stretches out 32mm from the end face of the other end of described electrode fixed mount 161;
The external diameter of silver cathode 8, wall thickness and length are respectively 16mm, 1.2mm and 43mm;
The diameter of filamentary silver 22 is 0.5mm.
The product of embodiment 4 and import like product (the polarogram formula electrode product of Switzerland Swan company) have carried out reaching six months on-the-spot test comparison test.The advantage of finding the product of embodiment 4 is to be quick on the draw; Be reflected in midnight especially during the power plant load peak regulation; Because of having slightly, the dissolved oxygen DO of the reduction boiler feedwater of power consumption rises; The instrument of Swan keeps showing that 0.5 μ g/L is constant, and the product of embodiment 4 is changed to 0.6～0.7 μ g/L by 0.5 μ g/L, and the data reappearance of the product of embodiment 4 is good under power plant's operating mode kilter.This is because the output current of the product of embodiment 4 is bigger, causes stable performance and highly sensitive cause.
The long-term service test of the product through embodiment 4, draw to draw a conclusion: 1, this product was not safeguarded once in nine months, explained that this product is very low to maintenance requirement.2, uninterrupted operate as normal is 1 year, and the measurement result of trace dissolved oxygen is still correct, explains that be not less than 1 year the serviceable life of this product.This is because adopt spongy lead cylinder 15 to increase the cause of the surface area of lead anode 9.3, the product of embodiment 4 is because the long-term accumulation corrosion that boiler feedwater produces makes and covers the orange-yellow sediment of cover one deck on its outer wall, but this product still can operate as normal, explains that this product has excellent antifouling property.From water, take out this product and to examine the back and find, on the surface of macromolecule membrane 7, still have many parts can get into oxygen, guarantee that this product still can operate as normal.This is because this product has used the relatively large silver cathode 8 of outer wall area, helps to improve its resistant to pollution performance.
Electrode of the present invention is suitable especially to be used for measuring or the trace dissolved oxygen of the boiler feedwater of on-line monitoring firepower power station or nuclear power station.
Claims (8)
1. an electrode of measuring trace dissolved oxygen contains cable tube joint (1), cable seal O shape rubber band (2), arc-spark stand (16), lead anode (9), silver cathode (8), electrolytic solution (10), macromolecule membrane (7), lock ring O shape rubber band (6), cylinder ring (12), electrolytic solution sealing O shape rubber band (110), fastening bolt (11), and cable tube joint (1) is the hollow nut of being processed by the PE material, is shaped on first screw thread (25) on the hitching post of this nut; Central part office at the cap of this nut has first cable aperture (24), and arc-spark stand (16) contains electrode fairlead (160) and electrode fixed mount (161), and electrode fairlead (160) is the pipe of being processed by the PE material, is shaped on the 3rd screw thread (165) and the 4th screw thread (164) on the inwall at the two ends of this pipe respectively; Have the inside with this pipe to be divided into two-part circular shim in this pipe, have at the core of this shim and connect described two-part second cable aperture (23), be shaped on measuring cell connector (3) on the outer wall of this pipe, this connector contains flange (30), watertight O shape rubber band (31) and second screw thread (32); Watertight O shape rubber band (31) hoop is enclosed within on the outer wall of the electrode fairlead (160) between flange (30) and second screw thread (32), and the parting face was that stepped appearance De rotation is turned during electrode fixed mount (161) was processed, indulged by the PE material, and an end of this fixed mount has a class, and the bus De rotation of this class changes the bus De rotation commentaries on classics radius of radius less than this fixed mount; On the cylinder that the De of this class rotation is turned, be shaped on the 5th screw thread (163), on the De of this class rotation is turned, be shaped on central shaft and the De of this class rotation cylindrical pitting that rotating shaft (0) overlaps of turning, the other end of this fixed mount has two classes, and the bus De rotation of first class changes radius and changes radius less than the bus De rotation of this fixed mount; On the cylinder that the De of this class rotation is turned, be shaped on the 6th screw thread (162), the bus De rotation of second class changes radius and changes radius less than the bus De rotation of first class, on the outer wall of this fixed mount, is shaped on the circular groove that twice are parallel to each other, and on this fixed mount, has the straight circular hole of bottom surface of end face and the described cylindrical pitting of the other end that runs through this fixed mount; The central shaft of this straight circular hole overlaps with the rotating shaft of this fixed mount (0), on this fixed mount, has oblique circular hole (166), and this oblique circular hole runs through annular plane and the bottom surface of described cylindrical pitting between the cylinder that the radius Jiao Da De rotation of the other end of the cylinder that is clipped in this fixed mount and this fixed mount turns, and lead anode (9) is the pole of being processed by lead; Silver cathode (8) is the silver pipe, and the inwall at the two ends of this pipe is shaped on the 7th screw thread (82) and the 8th screw thread (81) respectively, has many apertures that are uniformly distributed with (80) on the tube wall of this pipe; The ratio of the area summation of aperture (80) and silver electrode (8) outer wall area is between 1: 50～70, macromolecule membrane (7) be columnar, do not seep water but can see through the organic film of oxygen, cylinder ring (12) is the pipe of being processed by the PE material; The external diameter of one end of this pipe is less, at the tube wall of said end, on be shaped on the 9th screw thread (121); On the inwall of this pipe, be shaped on the tenth screw thread (120), on the outer wall of this pipe, be shaped on the circular groove that twice are parallel to each other, fastening bolt (11) is the bolt of being processed by the PE material; Be shaped on the 11 screw thread (111) on the hitching post of this bolt, lead anode (9) to be inserting above-mentioned straight circular hole with the above-mentioned friction tight mode of straight circular hole, and stretch out from the end face of the other end of the bottom surface of described cylindrical pitting and electrode fixed mount (161) respectively at the two ends of lead anode (9); Filamentary silver (22) is gone up at the 6th screw thread (162) and is twined a circle, and silver cathode (8) is screwed onto with electrode fixed mount (161) through the 7th screw thread (82) and the 6th screw thread (162), and filamentary silver (22) is clipped between silver cathode (8) and the electrode fixed mount (161); Pass oblique circular hole (166) after two terminations of filamentary silver (22) are stranded and stretch out from the bottom surface of described cylindrical pitting, the external diameter of silver cathode (8) equates that with the external diameter of electrode fixed mount (161) termination and the lead anode (9) of first heart yearn (18) of cable (20) are welded into anode soldering tip (4); The termination and the filamentary silver (22) of second heart yearn (17) of cable (20) are welded into negative electrode soldering tip (21), and electrode fairlead (160) is spirally connected into arc-spark stand (16) through the 4th screw thread (164) with the 5th screw thread (163) with electrode fixed mount (161) passes second cable aperture (23) with cable (20) mode, and cable tube joint (1) and electrode fairlead (160) pass the O shape hole of cable seal O shape rubber band (2) with cable (20) and the mode of second cable aperture (24) is screwed onto together through first screw thread (25) and the 3rd screw thread (165); Cylinder ring (12) and electrode fixed mount (161) are screwed onto together through the 8th screw thread (81) and the 9th screw thread (121), and the external diameter of cylinder ring (12) equates with the external diameter of electrode fixed mount (161), covers the macromolecule membrane (7) that is covered with the pipe shape on the outer wall of silver cathode (8); Each is close to the two ends of macromolecule membrane (7) it on circular groove that circular groove that twice on electrode fixed mount (161) are parallel to each other and the twice on the cylinder ring (12) are parallel to each other respectively with twice lock ring O shape rubber band (6), and filling is with electrolytic solution (10) in the space between lead anode (9) and silver cathode (8), and fastening bolt (11) seals O shape rubber band (110), the tenth screw thread (120) and the 11 screw thread (111) through electrolytic solution and is screwed onto with cylinder ring (12) with the mode that electrolytic solution (10) does not leak outside; It is characterized in that an end of the lead anode (9) that stretches out at the end face from the described other end of electrode fixed mount (161) is fixed with spongy lead cylinder (15), the central shaft of this cylinder overlaps with the central shaft of lead anode (9).
2. the electrode of measurement trace dissolved oxygen according to claim 1 is characterized in that, in described cylindrical pitting, is perfused with anode soldering tip (4) and negative electrode soldering tip (21) are locked in the epoxy resin (5) in the described cylindrical pitting.
3. the electrode of measurement trace dissolved oxygen according to claim 1 is characterized in that, epoxy resin (5) top has flowable state silicon rubber (50) and cure silicone rubber (51) successively.
4. the electrode of measurement trace dissolved oxygen according to claim 1 is characterized in that, electrolytic solution (10) is that concentration is the soda mint of 8wt%～10wt%.
5. the electrode of measurement trace dissolved oxygen according to claim 1; It is characterized in that; The external diameter of spongy lead cylinder (15) equates with the external diameter of the end face of the described other end of electrode fixed mount (161); On the cylinder of the outer wall of spongy lead cylinder (15) and the cylinder that contains said end face, cover and be covered with anode sheath (14), anode sheath (14) is the porous polymer materials that can pass through oxygen and electrolytic solution (10).
6. the electrode of measurement trace dissolved oxygen according to claim 1 is characterized in that,
The diameter and the length of spongy lead cylinder (15) are respectively 12mm and 37mm;
The diameter and the length of lead anode (9) are respectively 2mm and 45mm, and the one of which end stretches out 3mm from the bottom surface of described cylindrical pitting, and its other end stretches out 32mm from the end face of the other end of described electrode fixed mount (161);
The external diameter of silver cathode (8), wall thickness and length are respectively 16mm, 1.2mm and 43mm;
The diameter of filamentary silver (22) is 0.5mm.
7. according to the electrode of the described measurement trace dissolved oxygen of claim 1; It is characterized in that in described cylindrical pitting, be perfused with anode soldering tip (4) and negative electrode soldering tip (21) are locked in the epoxy resin (5) in the described cylindrical pitting, electrolytic solution (10) is that concentration is the soda mint of 8wt%～10wt%; The external diameter of spongy lead cylinder (15) equates with the external diameter of the end face of the described other end of electrode fixed mount (161); On the cylinder of the outer wall of spongy lead cylinder (15) and the cylinder that contains said end face, cover and be covered with anode sheath (14), anode sheath (14) is the porous polymer materials that can pass through oxygen and electrolytic solution (10), in space (19), fill with silica gel; The diameter and the length of spongy lead cylinder (15) are respectively 12mm and 37mm; The diameter and the length of lead anode (9) are respectively 2mm and 45mm, and the one of which end stretches out 3mm from the bottom surface of described cylindrical pitting, and its other end stretches out 32mm from the end face of the other end of described electrode fixed mount (161); The external diameter of silver cathode (8); Wall thickness and length are respectively 16mm, 1.2mm and 43mm, and the diameter of filamentary silver (22) is 0.5mm.
8. according to the electrode of the described measurement trace dissolved oxygen of claim 1, it is characterized in that, in described cylindrical pitting, be perfused with anode soldering tip (4) and negative electrode soldering tip (21) are locked in the epoxy resin (5) in the described cylindrical pitting; Epoxy resin (5) top has flowable state silicon rubber (50) and cure silicone rubber (51) successively; Electrolytic solution (10) is that concentration is the soda mint of 8wt%～10wt%, and the external diameter of spongy lead cylinder (15) equates with the external diameter of the end face of the described other end of electrode fixed mount (161), on the cylinder of the outer wall of spongy lead cylinder (15) and the cylinder that contains said end face, covers to be covered with anode sheath (14); Anode sheath (14) is can be through the porous polymer materials of oxygen and electrolytic solution (10); In space (19), fill with silica gel, the diameter and the length of spongy lead cylinder (15) are respectively 12mm and 37mm, and the diameter and the length of lead anode (9) are respectively 2mm and 45mm; The one of which end stretches out 3mm from the bottom surface of described cylindrical pitting; Its other end stretches out 32mm from the end face of the other end of described electrode fixed mount (161), the external diameter of silver cathode (8), and wall thickness and length are respectively 16mm; 1.2mm and 43mm, the diameter of filamentary silver (22) is 0.5mm.
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| CN2009100475777A CN101498681B (en) | 2009-03-13 | 2009-03-13 | Electrode for measuring trace dissolved oxygen |
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| CN108169302B (en) * | 2017-11-20 | 2020-05-12 | 深圳大学 | Three-electrode system and using method thereof |
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| CN109253398B (en) * | 2018-11-01 | 2019-09-03 | 燕山大学 | A kind of underwater oil pipeline dynamic monitoring method considering temporary steady-state performance |
| CN109778290B9 (en) * | 2019-04-01 | 2024-01-12 | 河南理工大学 | Soluble anode mechanism |
| CN110865106A (en) * | 2019-12-25 | 2020-03-06 | 广州商辉仪业智能科技股份有限公司 | Dissolved oxygen electrode adapter |
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