CN1164937C - Electrochemical sensor of dissolved hydrogen sulfide in extreme exvironment - Google Patents
Electrochemical sensor of dissolved hydrogen sulfide in extreme exvironment Download PDFInfo
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- CN1164937C CN1164937C CNB02111367XA CN02111367A CN1164937C CN 1164937 C CN1164937 C CN 1164937C CN B02111367X A CNB02111367X A CN B02111367XA CN 02111367 A CN02111367 A CN 02111367A CN 1164937 C CN1164937 C CN 1164937C
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Links
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- 239000004020 conductor Substances 0.000 claims description 17
- 239000004642 Polyimide Substances 0.000 claims description 15
- 229920001721 polyimide Polymers 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910000679 solder Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- 229910052946 acanthite Inorganic materials 0.000 abstract 5
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 abstract 5
- -1 polytetrafluoroethylene Polymers 0.000 abstract 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000011241 protective layer Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention discloses an electrochemical sensor for dissolving hydrogen sulfide under extreme environment. The electrochemical sensor comprises an Ag/Ag2S electrode and a metal/metal oxide reference electrode, wherein the Ag/Ag2S electrode is provided with a metal conducting wire, a polytetrafluoroethylene tube is arranged outside the conducting wire, epoxy resin containing silver is arranged between the metal conducting wire and the polytetrafluoroethylene tube, and an Ag/Ag2S film is covered at the end part of the Ag/Ag2S electrode; the metal/metal oxide reference electrode is provided with a metal wire, and the surface of the metal/metal oxide reference electrode is provided with an active oxide film. The Ag/Ag2S electrode made from the epoxy resin containing silver has the advantages of quick detecting response, high sensitivity, lower detecting limit, long service life, etc. The electrochemical sensor for dissolving hydrogen sulfide is widely applied to the fields of high temperature and high pressure chemical synthesis, the online detection, the long term monitoring, etc. of geological action and natural environment under the extreme environment of high temperature, high pressure, high radioactivity, high acidity, etc.
Description
Technical field
The present invention relates to sensor, relate in particular to a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure.
Background technology
Under reducing condition, dissolved hydrogen sulfide content is one of important chemical property of aqueous solution.Chemistry, chemical industry, medicine, material, etc. industry, the participation of sulphur is all arranged in many important synthetic reactions, the concentration of the dissolved hydrogen sulfide in the aqueous medium is the sign that degree is carried out in this type of reaction.On the other hand, the dissolved hydrogen sulfide concentration in the solution still is the important parameter of knowledge of natural environment environment and geologic function, as the procreation of microorganism under the reducing condition, and volcano, hydrothermal activity etc.Dissolved hydrogen sulfide detector in the past can only be worked under lower temperature, pressure mostly, the invention provides a kind of can be to the high temperature condition of high voltage from normal temperature and pressure, the electrochemical sensor of dissolved hydrogen sulfide concentration in real-time detection and the long term monitoring aqueous solution.
Summary of the invention
The purpose of this invention is to provide a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure.
It comprises Ag/Ag
2S electrode and metal/metal oxide contrast electrode; Said Ag/Ag
2The S electrode has plain conductor, and lead is provided with polyfluortetraethylene pipe outward, is provided with the argentiferous epoxy resin stuff between the two, and its end of probe is coated with Ag/Ag
2The S film; Said metal/metal oxide contrast electrode has tinsel, and its surface is provided with the activating oxide film.
Ag/Ag proposed by the invention
2The S electrode adopts conduction to contain silver epoxy and makes, and it is fast, highly sensitive to have a probe response, detects that thresold is low down, advantages such as long service life.This Ag/Ag
2S electrode and metal/metal oxide pH electrode volume are all very little, and have certain mechanical strength and toughness, have good working performance under the temperature of broadness, pressure condition, and related preparation method's technology are simple, with low cost, are easy to promote.By these two kinds of electrochemical sensors that electrode constitutes, can dynamically monitor from normal temperature and pressure to extreme environments such as high temperature high pressure in real time under the variation of dissolved hydrogen sulfide concentration.Be suitable for the dissolved hydrogen sulfide concentration in the monitoring aqueous medium in poisonous and harmful, hot environment.It also is suitable under above-mentioned extreme condition, and online detection and long term monitoring are carried out in geologic function and physical environment, as deep-sea detecting and volcano monitoring.
Description of drawings
Fig. 1 is the electrochemical sensor of dissolved hydrogen sulfide structural representation that is applicable to High Temperature High Pressure.
Among Fig. 1: 1.Ag/Ag
2S electrode, 2. pick-up unit, 3. metal/metal oxide contrast electrode, 4. polyfluortetraethylene pipe, 5. plain conductor, 6. argentiferous epoxy resin stuff, 7.Ag/Ag
2S film, 8. tinsel, 9. activating oxide film.
Embodiment
The electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure comprises Ag/Ag
2S electrode 1 and metal/metal oxide contrast electrode 3; Said Ag/Ag
2The S electrode has plain conductor 5, and lead is provided with polyfluortetraethylene pipe 4 outward, is provided with between the two to contain silver epoxy 6, and its end is coated with Ag/Ag
2S film 7; Said metal/metal oxide contrast electrode has tinsel 8, and its surface is provided with activating oxide film 9.
Said Ag/Ag
2Preparation method's step of S electrode is as follows:
1) internal diameter is 0.3～2 millimeter a polyfluortetraethylene pipe, injects from an end to contain silver epoxy, inserts plain conductor from the other end to epoxy resin, and epoxy resin at room temperature solidifies, and polishes with fine sandpaper.
2) above-mentioned polyfluortetraethylene pipe is hung vertically in fills Ag
+In the electroplating bath of KCN solution, be connected on the power cathode, one section annular filamentary silver is placed in above-mentioned polyfluortetraethylene pipe bottom 1～3 centimeters, be connected on the positive source, fed 8～12 μ A electric currents 30-60 minute, polyfluortetraethylene pipe is taken out and use distilled water flushing;
3) polyfluortetraethylene pipe is immersed the (NH of 0.1～0.5M concentration
4)
2In the S solution 2～6 minutes, use distilled water flushing after the taking-up.
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
Above-mentioned plain conductor is a kind of in platinum, gold, silver and the copper conductor.
Preparation method's step of metal/metal oxide contrast electrode is as follows:
1) cut-off directly is 0.1～1 millimeter a tinsel, polish with schmigel in the surface, to remove original oxidation film, in acetone or triclene, boil then, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning is more than 1 minute, take out the back and clean with distilled water, air-dry;
2) tinsel after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and cover with the solubility carbonate powder, crucible is put into muffle furnace be heated to 850～930 ℃, and constant temperature 1.5～5 hours, after taking-up is chilled to room temperature, with the carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert in 80～120 ℃ of baking ovens dry, its surface coverage thick 15～30 microns uniform oxide layers;
3) scrape off one section oxide skin(coating) at an end wiry.The plain conductor of on this end, burn-oning;
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 5～50% solution, be coated on the plain conductor this solution and the solder joint position, air-dry.
Above-mentioned material wiry is a kind of among Ti, Zr, Ir, W, Ru, the Pd.Oxide is an oxide of the same race wiry.The soluble carbon hydrochlorate is a kind of in lithium carbonate, sodium carbonate and the sal tartari.
The electrochemical sensor of dissolved hydrogen sulfide that the present invention proposes is by Ag/Ag
2S electrode and contrast electrode are formed, and from the galvanochemistry angle, sensor can be expressed as:
(Ag/Ag
2S)
H2S|H
2S，H
+，H
2O|(M|MO
x)
Ref (1)
(Ag/Ag herein
2S)
H2SBe the dissolved hydrogen sulfide exploring electrode, and (M|MO
x)
RefBe the metal/metal oxide electrode, when the electrode pairing of it and other type, can be used as the pH electrode, the detection of dissolved hydrogen sulfide, (M|MO
x)
RefPlay a part contrast electrode.Under given temperature, pressure, ionic strength conditions, the potential difference (PD) of measuring (Δ E) is dissolving H
2The function of S activity, according to this specific rule being expressed as:
R, F and T represent gas law constant, Faraday constant and temperature (° K), aH respectively herein
2O is the activity of water, E °
H2S, be Ag/Ag
2The normal potential of S electrode.
The Ag/Ag that the present invention proposes
2The S electrode has adopted and has contained silver epoxy, and representational commercially available prod is the epoxy resin that Switzerland Polyscience company produces, and code name is Epo-tek 415G.The PAD-54 type resin that similar homemade commodity produce for the Shanghai synthetic resin plant, the two performance is more or less the same.The plain conductor that inserts in the epoxy resin is preferably selected silver, gold, platinum or other noble metal lead for use, to improve the integral working of sensor.
Behind the epoxy resin cure, its surface finish is become smooth, smooth plane, so that electroplate.Silver-plated used electroplate liquid is routinely, and technical is well-known.After carrying out necessary preparation, will treat that plated electrode is connected on the negative pole, the silver-colored articulating that is used as anode constitutes current return on positive pole.Strength of current and conduction time all need be controlled in the specified scope, in order to avoid coating is blocked up.
After electroplating end, formed the bright and uniform silver layer on the surface of epoxy resin.Be immersed in (NH
4)
2Behind the S solution, its surface can form one deck Ag rapidly
2The S film, it is right to constitute following electrochemical reaction:
The electrode for preparing should be stored in the distilled water.As use the back function reduction, and can carry out activation processing, promptly, immerse 0.1～0.5M (NH then again with rare nitric acid flushing electrode
4)
2Among the S in the solution 2～6 minutes.
Studies show that, when tested pH value of aqueous solution from alkali condition S
2-The advantage district of ion drops to acid condition HS
-During the advantage district of ion, do not find that potential curve has any bending, three kinds of dissolved forms, i.e. S of this electrode pair sulfuretted hydrogen are described
2-Ion, H
2S and HS
-Ion all has very strong selectivity.
From used material, by containing the Ag/Ag that silver epoxy is made
2The S electrode can tolerate 120～160 ℃ high temperature, and intermittently serviceability temperature can reach 200 ℃.Survey in the higher fluid of temperature as need, the Ag/Ag that is made up of the plated film silver strip is used in suggestion
2The S electrode.Its method for making is as follows:
1) cut-off directly is 0.2～2 millimeter a silver-colored lead, and at one end weldering lastblock silver strip, silver strip is of a size of: thickness is 0.1～0.4 millimeter, and length is 5～8 millimeters, and width is 2～5 millimeters;
2) end that will be welded with silver strip boils in acetone or triclene, to remove organic impurities, immerses the salpeter solution that concentration is 0.5～1M again, and ultrasonic cleaning is taken out the back and cleaned with distilled water;
3) silver strip after will cleaning is at 0.1～0.5M (NH
4)
2Soaked in the S solution 2～6 minutes, and made the silver strip surface form one deck Ag
2The S mocromembrane is used distilled water flushing once more.
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 5～50% solution, this solution is coated on the silver-colored lead, air-dry.
The Ag/Ag that makes with the argentiferous epoxide resin material
2The S electrode is compared, the electrode of forming by the plated film silver strip temperature than low environment in serviceability relatively poor, but it can be worked in temperature is up to supercritical fluid more than 400 ℃.Suggestion is used the former in temperature is lower than 200 ℃ environment; In being higher than 200 ℃ environment, temperature uses the latter.
Metal/metal oxide electrode material therefor is the stable tinsel of chemical property, as titanium, zirconium, iridium, tungsten, ruthenium and palladium silk.Length wiry can be determined according to the electrode size needs and the two aspect factors that are easy to process, be generally 0.6～1.2 centimeter length.Under the prerequisite that ensures required physical strength, select for use thinner tinsel to help reducing cost, and dwindle the size of electrode.Diameter wiry generally should be between 0.1～1 millimeter.
With the key that these metals are made the pH electrode, be to form the oxidation film that is suitable for electrochemical measurement in wire surface.Studies show that, the oxidation film that wire surface forms naturally, and simply tinsel is heated formed oxidation film in air, all can't be competent at electrochemical mensuration.Therefore, as the first step of making electrode, be to remove the original oxidation film of wire surface.The method that the present invention adopts mechanical grinding and chemical cleaning to combine.The former also available blasting treatment, the latter is divided into that organic solvent cleans and the acid solution cleaning, and the order of the two is unimportant.
Making another key of metal/metal oxide electrode, is will coat one deck in wire surface can see through H
+The activating oxide film of ion.It is the heating of medium that the present invention has adopted with carbonate.Wherein heating-up temperature should be higher than the fusing point of selected carbonate, should guarantee also that simultaneously carbonate does not have tangible decomposition in constant temperature time.The fusing point of three kinds of carbonate and the heating-up temperature of recommendation are respectively:
| Carbonate | Fusing point | Heating-up temperature |
| Li 2CO 3 | 723℃ | 850-870℃ |
| Na 2CO 3 | 851℃ | 880-900℃ |
| K 2CO 3 | 891℃ | 910-930℃ |
The constant temperature time of tinsel in the carbonate melt should be made corresponding adjustment according to the relative chemical activity of different metal.The constant temperature time that the present invention recommends (hour) be:
| Metal | Ti | Zr | Ru | W | Pd | Ir |
| Time | 1.5 | 1.5-2.0 | 3.0-3.5 | 3.0-3.5 | 4.0-4.5 | 5.0 |
All selected for use polyimide as the insulating protective layer that connects lead with top electrode, be because it is easy to coating, and have heat-resisting quantity preferably, polyimide can be no more than the medium-term and long-term use of 260 ℃ of environment in temperature, and intermittently serviceability temperature can reach 480 ℃.In addition, also can select for use teflon and organosilicon as insulating protective layer.Teflon has good heat-resistance equally, can be under 300 ℃ of temperature use for a long time, but that it molten, insoluble is difficult to it is processed.Organosilicon also has better heat-resisting and stability, uses more convenient.
Below in conjunction with embodiment the present invention is elaborated.
Example 1: make Ag/Ag with containing silver epoxy
2The S electrode
1) internal diameter is 2 millimeters a polyfluortetraethylene pipe, injects from an end to contain silver epoxy, inserts silver-colored lead from the other end to epoxy resin, and epoxy resin at room temperature solidifies, and polishes with fine sandpaper.
2) above-mentioned polyfluortetraethylene pipe is hung vertically in fills Ag
+In the electroplating bath of KCN solution, be connected on the power cathode, one section annular filamentary silver is placed in above-mentioned polyfluortetraethylene pipe bottom 1～3 centimeters, be connected on the positive source, fed 10 μ A electric currents 45 minutes, polyfluortetraethylene pipe is taken out and uses distilled water flushing;
3) polyfluortetraethylene pipe is immersed 0.3M (NH
4)
2In the S solution 2 minutes, use distilled water flushing after the taking-up.
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 30% solution, this solution is coated on the tinsel, air-dry.
Example 2: make Ag/Ag with the plated film silver strip
2The S electrode
1) cut-off directly is 0.5 millimeter a filamentary silver, and at one end weldering lastblock silver strip, silver strip is of a size of: thickness is 0.25 millimeter, and length is 6 millimeters, and width is 3 millimeters;
2) end that will be welded with silver strip boils in acetone, to remove organic impurities, immerses the salpeter solution that concentration is 0.5M again, and ultrasonic cleaning is taken out the back and cleaned with distilled water;
3) silver strip after will cleaning is (the NH of 0.3M in concentration
4)
2Soaked in the S solution 2 minutes, and made the silver strip surface form one deck Ag
2The S mocromembrane is used distilled water flushing once more.
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 30% solution, this solution is coated on the silver-colored lead, air-dry.
Example 3: make Ti/TiO
2Contrast electrode
1) cut-off directly is 0.3 millimeter a Ti silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Ti silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Ti silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 1.5 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ti silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ti silk.The diameter of burn-oning on this end is 0.1 millimeter a silver-colored lead;
4) be that 30% polyimide solution is coated on silver-colored lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 4: make Zr/ZrO
2Contrast electrode
1) cut-off directly is 0.3 millimeter a Zr silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the Zr silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the Zr silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 2 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Zr silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Zr silk.The diameter of burn-oning on this end is 0.1 millimeter a silver-colored lead;
4) be that 30% polyimide solution is coated on silver-colored lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 5: make W/WO
3Contrast electrode
1) cut-off directly is 0.3 millimeter a W silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the W silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the W silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 3 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the W silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of W silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 6: make Ir/IrO
2Contrast electrode
1) cut-off directly is 0.15 millimeter an Ir silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the Ir silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the Ir silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 5 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ir silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ir silk.The diameter of burn-oning on this end is 0.1 millimeter a platinum lead;
4) be that 30% polyimide solution is coated on the platinum lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 7: make Ru/RuO
2Contrast electrode
1) cut-off directly is 0.15 millimeter a Ru silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Ru silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Ru silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 3.5 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ru silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ru silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 8: make the Pd/PdO contrast electrode
1) cut-off directly is 0.15 millimeter a Pd silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Pd silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Pd silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 4 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Pd silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Pd silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, repeat for several times, so far electrode completes.
Claims (7)
1. an electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure is characterized in that it comprises Ag/Ag
2S electrode [1] and metal/metal oxide contrast electrode [3]; Said Ag/Ag
2The S electrode has plain conductor [5], and lead is provided with polyfluortetraethylene pipe [4] outward, is provided with argentiferous epoxy resin stuff [6] between the two, and its end of probe is coated with Ag/Ag
2S film [7]; Said metal/metal oxide contrast electrode has tinsel [8], and its surface is provided with activating oxide film [9].
2. a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure according to claim 1 is characterized in that said Ag/Ag
2Preparation method's step of S electrode is as follows:
1) internal diameter is 0.3～2 millimeter a polyfluortetraethylene pipe, injects from an end to contain silver epoxy, inserts plain conductor from the other end to epoxy resin, and epoxy resin at room temperature solidifies, and polishes with fine sandpaper;
2) above-mentioned polyfluortetraethylene pipe is hung vertically in fills Ag
+In the electroplating bath of KCN solution, be connected on the power cathode, one section annular filamentary silver is placed in above-mentioned polyfluortetraethylene pipe bottom 1～3 centimeters, be connected on the positive source, fed 8～12 μ A electric currents 30-60 minute, polyfluortetraethylene pipe is taken out and use distilled water flushing;
3) polyfluortetraethylene pipe is immersed the (NH of 0.1～0.5M concentration
4)
2In the S solution 2～6 minutes, take out the back distilled water flushing;
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
3. a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure according to claim 2 is characterized in that, said plain conductor is a kind of in platinum, gold, silver and the copper conductor.
4. a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure according to claim 1 is characterized in that, preparation method's step of said metal/metal oxide contrast electrode is as follows:
1) cut-off directly is 0.1～1 millimeter a tinsel, polish with schmigel in the surface, to remove original oxidation film, in acetone or triclene, boil then, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning is more than 1 minute, take out the back and clean with distilled water, air-dry;
2) tinsel after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and cover with the solubility carbonate powder, crucible is put into muffle furnace be heated to 850～930 ℃, and constant temperature 1.5～5 hours, after taking-up is chilled to room temperature, with the carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert in 80～120 ℃ of baking ovens dry, its surface coverage thick 15～30 microns uniform oxide layers;
3) scrape off one section oxide skin(coating) at an end wiry, the plain conductor of on this end, burn-oning;
4) soluble polyimide is dissolved in the organic solvent, is mixed with concentration and is 5～50% solution, be coated on the plain conductor this solution and the solder joint position, air-dry.
5. according to claim 1 or 4 described a kind of electrochemical sensor of dissolved hydrogen sulfide that are applicable to High Temperature High Pressure, it is characterized in that said material wiry is Ti, Zr, Ir, W, Ru, a kind of among the Pd.
6. according to claim 1 or 4 described a kind of electrochemical sensor of dissolved hydrogen sulfide that are applicable to High Temperature High Pressure, it is characterized in that said oxide is an oxide of the same race wiry.
7. a kind of electrochemical sensor of dissolved hydrogen sulfide that is applicable to High Temperature High Pressure according to claim 4 is characterized in that, said soluble carbon hydrochlorate is a kind of in lithium carbonate, sodium carbonate and the sal tartari.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006099799A1 (en) * | 2005-03-21 | 2006-09-28 | Ronghua Zhang | Zr/ZrO2 ELECTRODE AND PRODUCING METHOD THEREOF AND INTEGRATED HIGH TEMPERATURE AND HIGH- PRESSURE CHEMICAL SENSOR COMPOSED BY THE SAME |
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| CN102507682B (en) * | 2011-10-27 | 2013-09-18 | 浙江大学 | Dissolved hydrogen sulfide detection electrode based on silver/nano silver and preparation method for dissolved hydrogen sulfide detection electrode |
| AU2012397897A1 (en) * | 2012-12-28 | 2015-07-23 | Outotec (Finland) Oy | Method and apparatus for monitoring the quality of ore |
| CN103196971A (en) * | 2013-03-28 | 2013-07-10 | 浙江大学 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| CN104749231A (en) * | 2015-04-01 | 2015-07-01 | 合肥工业大学 | Electrochemical sensor and application thereof in rapid detection for hydrogen sulphide |
| CN108802107B (en) * | 2017-05-02 | 2021-02-09 | 中国石油化工股份有限公司 | Method for measuring concentration of hydrogen sulfide based on resistance |
| CN108760862B (en) * | 2018-04-04 | 2020-09-01 | 山东特检科技有限公司 | Silver bromide electrode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006099799A1 (en) * | 2005-03-21 | 2006-09-28 | Ronghua Zhang | Zr/ZrO2 ELECTRODE AND PRODUCING METHOD THEREOF AND INTEGRATED HIGH TEMPERATURE AND HIGH- PRESSURE CHEMICAL SENSOR COMPOSED BY THE SAME |
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