CN1123411A - Probe for quick determination of silicon content in molten iron - Google Patents
Probe for quick determination of silicon content in molten iron Download PDFInfo
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- CN1123411A CN1123411A CN 94118335 CN94118335A CN1123411A CN 1123411 A CN1123411 A CN 1123411A CN 94118335 CN94118335 CN 94118335 CN 94118335 A CN94118335 A CN 94118335A CN 1123411 A CN1123411 A CN 1123411A
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Abstract
The method is based on the principle of concentration cell to determine the silicon content in molten iron. Its probe comprises mainly the addition of auxiliary electrde spots uniformly distributed onthe surface of the solid dielectric, their compositions are ZrSiO4 and ZrO2, the thickness of the spots is 2-3mm, diameter is 2-3mm, their area is 70-80% that of the solid dielectric, sintering temp. is 1550-1610 deg.C constantly keeping for 30-80 min. Advantage: simple structure, easy and quick operation, high accuracy, high success rate and high reproduction rate.
Description
The present invention belongs to the field of material analysis technology by measuring chemical and physical properties of material.
With the improvement of the quality of steel, a converter requires smelting under the condition of less slag or no slag, and for this reason, the silicon content of the steel-making pig iron produced by a blast furnace is required to be as low as possible and is gradually reduced to about 0.50 percent of the silicon content. Therefore, a high furnace is required to have a high operation level and stable furnace conditions, the silicon content in pig iron needs to be determined timely and accurately to ensure the production of pig iron with low silicon content, and meanwhile, the technology of dephosphorization treatment outside the molten iron furnace also needs to accurately and timely control the silicon content in pig iron so as to scientifically add the dephosphorization agent and accurately control the dephosphorization process. At present, the traditional chemical analysis method which is generally adopted has long time for sampling and analyzing, so that the stable control of the silicon amount in the molten iron and the optimal external molten iron treatment process condition are difficult to realize, thereby being difficult to adapt to the requirement of modern production of high-quality pig iron.
The fast silicon determining probe for molten iron is suitable for blast furnace production and is developed through direct insertion of molten iron to determine the silicon content in pig iron fast and accurately. At present, the molten iron rapid silicon determination measuring head is a thermoelectromotive force method, a plurality of standard curves for comparison are required to be set in the method, the structure is complicated, and the manufacturing difficulty is high. The quick oxygen-determining probe for molten steel is an oxygen concentration cell, and is inserted into the molten steel to form [ O ] | | ZrO2.MgO||Mo，MoO2The oxygen potential of the battery is determined by the positive electrode of the battery on the right side and the negative electrode of the battery on the left side Reaction and solid electrolyte (ZrO)2MgO) and the partial pressure of oxygen at the interface with the molten steel. Therefore, as long as the electromotive force and the corresponding temperature of the battery are measured, the oxygen activity of the molten steel can be measured.
The invention aims to overcome the defects of long sampling and chemical analysis time and low speed of a chemical analysis silicon determination method and the defects of complicated structure and difficult manufacture of a thermoelectrical potential method. By applying the principle of the solid electrolyte rapid oxygen determination probe, the spot-shaped auxiliary electrode is added on the outer surface of the solid electrolyte tube of the molten steel rapid oxygen determination probe to form the molten iron rapid silicon determination probe. Inserting the measuring head into the molten iron, measuring the electromotive force and the working temperature of the solid electrolyte battery to obtain the activity of silicon in the molten iron, and calculating the silicon content in the molten iron according to the average composition of the molten iron. After the probe is inserted into the molten iron, the potential is obtained for 20 seconds, and the silicon content in the iron is obtained for 1 minute.
The invention inserts the quick silicon determination probe into the molten iron to form the following battery
〔Si〕Fe|C D||ZrO2·Mgo||Mo，MoO2Right side Mo, MoO in the battery2Being positive, the oxygen partial pressure of which depends on the following reaction equilibrium
The left side of the cell is the negative electrode, whose oxygen content is determined by the solid electrolyte (Zr)2O.MgO), the auxiliary electrode (CD) and the oxygen partial pressure at the three-phase interface of the molten iron are determined mainly by the following reaction equilibrium ① or ② the relationship of battery electromotive force can be derived from the aboveOr
In the formula, Pe' -electronic conduction characteristic oxygen partial pressure of solid electrolyte, E-battery potential
T-cell operating temperature
F-Faraday constant
R-gas constant
ΔG1 OStandard free enthalpy change of reaction ①
ΔG2 OStandard free enthalpy change of reaction ②
The invention relates to an oxygen concentration cell, wherein on the molten iron side, the oxygen partial pressure on three interfaces of molten iron, solid electrolyte and auxiliary electrode depends on the oxygen activity and the silicon activityThe balance between the degrees is established on a three-phase interface due to the addition of the auxiliary electrode, so that the invention inserts the rapid silicon determination measuring head into the molten iron, and the silicon activity a in the molten iron can be obtained as long as the electromotive force and the working temperature of the battery are measuredsiAnd calculating the silicon content in the molten iron according to the average composition of the molten iron.
The invention discloses a rapid silicon determination probe which is illustrated in a drawing, and comprises a slag-proof cap (1), an auxiliary electrode (CD) (2), a zirconia tubular solid electrolyte (3), a reference electrode (a battery anode) (4), a molybdenum wire (5), alumina powder (6), refractory fiber cotton (8), high-temperature cement (9), a refractory mud head (10), a large paper tube (11), a plastic tube (12), a copper lead (13), a small paper tube (14), a plastic socket (15), a plug outer sleeve (16), a plug copper ring (17), a plug insulating seat (18), an insulating lead (19), a plug insulating ring (20), a copper lead (21), a molybdenum rod (23) and a micro thermocouple (24).
The invention relates to a probe structure for rapidly determining silicon, which comprises a zirconia tubular solid electrolyte, wherein a CD is an auxiliary electrode of a battery and is ZrSiO4And ZrO2The positive electrode of the electrode is a reference electrode (Mo/MoO)2) Alumina powder, molybdenum wire, refractory fiber cotton, high-temperature cement and refractory clay head, solid electrolyte (ZrO)2MgO) tube having an outer wall surface of spot-sintered auxiliary electrode (ZrSiO)4·ZrO2) The spot-shaped auxiliary electrode has the thickness of 2-3mm and the diameter of 2-3mm, occupies about 70-80% of the surface area of the negative electrode of the battery, and is provided with a molybdenum rod, a micro thermocouple and the like. In solid electrolyte batteries, molybdenum rods and miniature thermocouplesCement filler is filled between the two parts, copper leads of the molybdenum wire, the micro thermocouple and the molybdenum rod are correspondingly led out, and the copper leads are connected with a small paper tube, an inner plastic sleeve socket, a plug insulating ring, a plug insulating seat, an insulating lead, a plug outer sleeve, a large paper tube and the like after being isolated by the cement filler.
The invention adopts the solid electrolyte zirconium oxide (ZrO) bonded with the auxiliary electrode2MgO) to form the negative electrode of the battery, an auxiliary electrode bonded to the outer surface of the zirconia tube, an auxiliary electrodeThe electrode material is ZrSiO4And ZrO2Or alternatively SiO2The auxiliary electrode material is fine powder with a tensile degree of less than 0.075mm, the low-temperature bonding material of the auxiliary electrode material is glycerol, the addition amount of the glycerol is about 1% of the mass of the auxiliary electrode, and the high-temperature bonding agent is CaF2，Al2O3The adding amount is 1-8% of the mass of the auxiliary electrode material.
The invention uses zirconium silicate (ZrSiO)4) And zirconium oxide (ZrO)2) Mixing the fine powder uniformly according to a certain proportion, and mixing the low-temperature adhesive glycerol and the high-temperature adhesive Al2O3Or CaF2The auxiliary electrode material is uniformly mixed according to 1-8% of the mass of the auxiliary electrode material, and is mixed with the auxiliary electrode material into paste, and the paste is distributed on the outer surface of the solid electrolyte zirconia tube in the form of spots, and the spots of the auxiliary electrode account for 70-80% of the surface area of the solid electrolyte tube. Then the zirconia tube adhered with the auxiliary electrode material is placed in a heating furnace, the temperature is raised to 1550-1610 ℃, the constant temperature is kept for 30-180 minutes, and then the zirconia tube is cooled to the room temperature, wherein the sintering temperature and the sintering time are determined according to the auxiliary electrode material and the adhesive type.
The invention relates to an auxiliary electrode material zirconium silicate (ZrSiO)4) And zirconium oxide (ZrO)2) The fine powder can be uniformly mixed according to the mass ratio of 1: 1. The low temperature binder may be glycerol.
In the embodiment 1 of the invention, the auxiliary electrode material is ZrSiO4And ZrO2The particle size of the mixture of (1) and (3) is 0.075mm, the mass ratio of the two materials is 1: 1, the low-temperature binder is glycerol, and the mass of the auxiliary electrode material is 1%. The high-temperature binder is GaF2Fine powder with a ratio of 2% of the auxiliary electrode material, an auxiliary electrode spot thickness of 2mm and a diameter of 2mm is uniformly distributed on the surface of the solid electrolyte, the area of the fine powder is 70% of the surface area of the solid electrolyte, and the sintering temperature is1560 deg.C, and sintering time is about 1 hr.
In the embodiment 2 of the invention, the auxiliary electrode material is ZrSiO4And ZrO2The mixture of (1) and (2) has a particle size of 0.075mm, a mass ratio of the two materials of 1: 1, and the low-temperature binder is glycerolAbout 1 percent of the mass of the auxiliary electrode material, and Al as a high-temperature binder2O3The amount of the fine powder added is 3% of the mass of the auxiliary material, the diameter of the auxiliary electrode spot is 2mm, the spot thickness is 2.5mm, the fine powder accounts for 70% of the surface of the solid dielectric, the sintering temperature is 1540 ℃, and the sintering time is 1.5 hours.
In the embodiment 3 of the invention, the auxiliary electrode material is SiO2The granularity is 0.075mm, the low-temperature adhesive is 1 percent of glycerol, and the high-temperature adhesive is Al2O3The amount of the fine powder added was 4%, and the diameter of the auxiliary electrode spot was 2 mm. The spots are 3mm in thickness, are uniformly distributed on the surface of the solid electrolyte and account for 80 percent of the surface of the solid electrolyte, the sintering temperature is 1560 ℃, and the sintering time is 2.5 hours.
The probe for quickly determining the silicon in the molten iron is used for determining the silicon in the molten iron, other components do not have large fluctuation, the silicon content in the molten iron is measured to be 0.1-1.5%, the platform duration is more than or equal to 4 seconds, the response time is less than or equal to 2 seconds, the accuracy is less than or equal to +/-0.02% Si, the reproducibility is less than or equal to +/-3 mV, and the measurement yield is more than or equal to 90%. Using input impedance of related meter > 106Ohm, double arm electronic balancing instrument, can measure the thermoelectrical potential and electromotive force at the same time, the measuring range of electromotive force is 0-1000 mV.
The invention has simple structure, easy operation, wide measuring range, accuracy, short response time, high repeatability and high measuring rate, and is suitable for quickly determining silicon in molten iron.
Claims (5)
1. The probe for quickly determining silicon content in molten iron comprises a zirconia tube and a reference electrode (MoMoO)2) Corundum capillary tubes, molybdenum rods. Molybdenum wire, micro thermocouple, characterized by solid electrolyte (ZrO)2MgO) tube, wherein spot-shaped sintered auxiliary electrodes are bonded on the outer wall surface of the MgO) tube, the spot thickness is 2-3mm, the diameter is 2-3mm, the area occupied by the spot-shaped auxiliary electrodes is 70-80% of the surface area of the outer wall of the solid electrolyte tube, and the auxiliary electrode material is ZrSiO4，ZrO2Or is SiO2Fine powder with 0.075mm particle size, and low-temperature binder of 1 mass of glycerol as auxiliary electrode materialPercent, high temperature Binder CaF2， A12O3Accounting for 1-8% of the mass of the auxiliary electrode material. Mixing the auxiliary electrode material containing the high-temperature adhesive into paste by using glycerol, adhering the paste on the surface of the solid dielectric medium in a spot shape, heating to 1500-.
2. The probe for rapidly determining the silicon content in the molten iron according to claim 1, wherein the auxiliary electrode material is zirconium silicate (ZrSiO)4) And zirconium oxide (ZrO)2) The fine powder can be uniformly mixed according to the mass ratio of 1: 1.
3. The probe for rapidly determining the silicon content in the molten iron according to claim 1, wherein the auxiliary electrode material ZrSiO is used as the auxiliary electrode material4And ZrO2The low-temperature binder is glycerol, the addition amount of the low-temperature binder is 1 percent of the mass of the auxiliary electrode material, and the high-temperature binder is CaF2The addition amount of the fine powder is 2 percent of the mass of the auxiliary electrode material, the auxiliary electrode spots are 2mm in thickness and 2mm in diameter and are uniformly distributed on the surface of the dielectric medium, the occupied area of the fine powder is 70 percent of the surface area of the solid electrolyte, the sintering temperature is 1560 ℃, and the sintering time is about 1 hour.
4. The molten iron rapid silicon determination probe according to claim 1 or 2, characterized in that the low temperature binder is glycerol accounting for about 1% of the mass of the auxiliary electrode material, and the high temperature binder is Al2O3Fine powder accounting for 3% of the mass of the auxiliary material, the diameter of the auxiliary electrode spot being 2mm, the thickness of the spot being 2.5mm and accounting for 70% of the surface area of the solid electrolyte,the sintering temperature was 1540 ℃ and the sintering time was 1.5 hours.
5. The molten iron rapid silicon determination probe according to claim 1, wherein the low temperature binder is glycerol, the addition amount is 1% of the auxiliary electrode material, and the high temperature binder is Al2O3Fine powder with a mixing amount of 4%, auxiliary electrode spot diameter of 2mm and spot thickness of 3mm, uniformly distributed on the surface of solid medium at 80%, sintering temperature of 1560 deg.C, and sinteringThe junction temperature was 2.5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118335 CN1123411A (en) | 1994-11-22 | 1994-11-22 | Probe for quick determination of silicon content in molten iron |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118335 CN1123411A (en) | 1994-11-22 | 1994-11-22 | Probe for quick determination of silicon content in molten iron |
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| CN1123411A true CN1123411A (en) | 1996-05-29 |
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| CN 94118335 Pending CN1123411A (en) | 1994-11-22 | 1994-11-22 | Probe for quick determination of silicon content in molten iron |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206728A (en) * | 2011-05-27 | 2011-10-05 | 上海普拉博冶金检测探头有限公司 | Phosphorus detection component on phosphorus detection probe for detecting phosphorus content in molten steel |
| CN101765767B (en) * | 2007-06-29 | 2013-06-12 | 代表亚利桑那大学的亚利桑那校董会 | Electrochemical detection of silica species |
| CN104845414A (en) * | 2015-05-04 | 2015-08-19 | 武汉科技大学 | Coating for silicon determination sensor auxiliary electrode and preparation method thereof |
| CN108918615A (en) * | 2018-07-19 | 2018-11-30 | 东北大学 | A kind of electrochemical sensor and preparation method thereof measuring manganese in molten steel/iron liquid |
-
1994
- 1994-11-22 CN CN 94118335 patent/CN1123411A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765767B (en) * | 2007-06-29 | 2013-06-12 | 代表亚利桑那大学的亚利桑那校董会 | Electrochemical detection of silica species |
| CN102206728A (en) * | 2011-05-27 | 2011-10-05 | 上海普拉博冶金检测探头有限公司 | Phosphorus detection component on phosphorus detection probe for detecting phosphorus content in molten steel |
| CN104845414A (en) * | 2015-05-04 | 2015-08-19 | 武汉科技大学 | Coating for silicon determination sensor auxiliary electrode and preparation method thereof |
| CN108918615A (en) * | 2018-07-19 | 2018-11-30 | 东北大学 | A kind of electrochemical sensor and preparation method thereof measuring manganese in molten steel/iron liquid |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Co-applicant after: Hangzhou Iron & Steel Group Company Co-applicant before: Hangzhou Iron and Steel orks |
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| CB03 | Change of inventor or designer information |
Inventor after: Zhang Qianxiang Inventor after: Qin Honglai Inventor after: Ren Weici Inventor after: Wu Peiliang Inventor after: Song Jiancheng Inventor after: Hong Yanruo Inventor after: Xue Chaoyun Inventor after: Huang Yanling Inventor after: Jia Chengke Inventor before: Zhang Qianxiang Inventor before: Qin Honglai Inventor before: Wu Peiliang Inventor before: Song Jiancheng Inventor before: Hong Yanruo Inventor before: Xue Chaoyun Inventor before: Huang Yanling Inventor before: Jia Chengke |
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| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHANG QIANXIANG; QIN HONGLAI; WU PEILIANG; SONG JIANCHENG; HONG YANRUO; XUE ZHAOYUN; HUANG YANLING; JIA CHENGKE TO: ZHANG QIANXIANG; QIN HONGLAI; REN WEICI; WU PEILIANG; SONG JIANCHENG; HONG YANRUO; XUE ZHAOYUN; HUANG YANLING; JIA CHENGKE; CO-APPLICANT; FROM: HANGZHOU IRON AND STEEL FACTORY TO: HANGZHOU IRON AND STEEL GROUP CORP. |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |