CN114486858B - Determination of TiO in blast furnace slag2Method of activity - Google Patents
Determination of TiO in blast furnace slag2Method of activity Download PDFInfo
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- 230000000694 effects Effects 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 claims abstract description 245
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 40
- 239000010439 graphite Substances 0.000 claims abstract description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 9
- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 229910002974 CaO–SiO2 Inorganic materials 0.000 claims description 3
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 claims description 3
- 229910017970 MgO-SiO2 Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000012935 Averaging Methods 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps: adding metallic tin, a reference slag sample and a slag sample to be detected into a six-hole graphite crucible; placing the six-hole graphite crucible into a tube furnace; heating the sample temperature of the tube furnace to 1500+/-2 ℃, preserving heat for 20-30 hours, and taking out the six-hole graphite crucible for quenching; taking out the cooled reference slag sample and the slag sample to be detected, and polishing and preparing the slag sample respectively; respectively analyzing mass fractions of Ti in Sn when the reaction is balanced for the prepared slag sample to be detected and the reference slag sample; respectively calculating x [Ti] and x ref[Ti]; from the formulaAnd calculating to obtain the activity of TiO 2 in the slag sample to be detected. The method for measuring the activity of TiO 2 in blast furnace slag provided by the invention is simple and high in measurement accuracy.
Description
Technical Field
The invention relates to the technical field of physical and chemical tests, in particular to a method for measuring the activity of TiO 2 in blast furnace slag.
Background
In the blast furnace smelting process, as titanium is harder to reduce than iron, almost all titanium enters a slag phase, titanium-containing blast furnace slag with the mass fraction of TiO 2 being more than 20% is formed, and the method has important significance for realizing the comprehensive utilization of the titanium-containing blast furnace slag, enriching an activity database and the like for measuring the activity of titanium-containing blast furnace slag components.
How to measure the activity of a component is an important direction for researching the thermodynamic performance of the component, but is influenced by the complexity of high-temperature experiments and the precision of experimental data, and is very difficult to measure the activity of the component currently. The prior method for measuring the activity of the components in the blast furnace slag mainly comprises a chemical equilibrium method, an electromotive force method, a vapor pressure method, a distribution equilibrium method, a G-D formula calculation method, a partial molar thermodynamic function calculation method and the like. Because of the complexity of high temperature experiments and the precision of experimental data, thermodynamic data are often required to be quoted when the activity of the components is experimentally measured by methods such as a chemical equilibrium method, an electromotive force method, a vapor pressure method, a distribution equilibrium method, a G-D formula calculation method, a partial molar thermodynamic function calculation activity method and the like, and the inaccuracy of the experimental data is easily caused.
Therefore, a method for effectively improving the accuracy of experimental data for determining the activity of TiO 2 in blast furnace slag is needed at present, and measurement errors easily caused by other methods because thermodynamic data need to be cited are avoided.
Disclosure of Invention
The invention aims to provide a method for measuring the activity of TiO 2 in blast furnace slag, which has the advantages of simple measurement method and high measurement accuracy.
In order to solve the technical problems, the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps:
Putting equal mass metal tin into each hole of a six-hole graphite crucible, putting a reference slag sample into one hole, and respectively putting to-be-detected slag samples with the same amount as the reference slag sample into the other five holes;
heating a tubular furnace sample to 700-800 ℃, removing air in a furnace tube, introducing CO, and then placing the six-hole graphite crucible into the tubular furnace;
heating the sample temperature of the tube furnace to 1500+/-2 ℃, preserving heat for 20-30 hours, and taking out the six-hole graphite crucible for quenching;
taking out the cooled reference slag sample and the slag sample to be detected, and polishing and preparing the slag sample respectively;
respectively analyzing the prepared slag sample to be detected and the reference slag sample to obtain the mass fraction of [ Ti ] in Sn when the reaction of the slag sample to be detected and the reference slag sample is balanced;
Respectively calculating x [Ti] and x ref[Ti] from mass fractions of [ Ti ] in Sn when the reaction balance of the slag sample to be detected and the reference slag sample is carried out;
From the formula Calculating to obtain the activity of TiO 2 in the slag sample to be detected;
wherein x ref[Ti] is the mole fraction of [ Ti ] in Sn at the reference slag sample reaction equilibrium, and x [Ti] is the mole fraction of [ Ti ] in Sn at the slag sample reaction equilibrium to be detected.
Further, the reference slag is CaF 2-TiO2 slag system.
Further, the reference slag comprises, by mass, 30% of CaF 2 and 70% of TiO 2.
Further, the slag to be detected is one of blast furnace type slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3-CaO and TiO 2-SiO2-Al2O3 -CaO-MgO slag system.
Further, the formulaThe deduction method of (2) comprises the following steps:
The reaction of TiO 2 in the slag to be detected is as follows:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g)
The reaction of TiO 2 in the reference slag is as follows:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g)
In the method, in the process of the invention, And/>Respectively taking pure substances as the activities of TiO 2 in the slag to be detected and the reference slag in a standard state; a [Ti] and a ref[Ti] are respectively the activities of Ti in Sn when the reaction of the slag to be detected and the reference slag is balanced by taking the imaginary pure substances as standard states; p CO and p θ are the partial pressure of CO and the normal atmospheric pressure, respectively;
Because the reaction of the slag to be detected and the reference slag is carried out under the same condition, when the activity standard states of the corresponding components are the same, K 2＝K4 is as follows:
Since a [Ti]＝f[Ti]·x[Ti]、aref[Ti]＝f[Ti]·xref[Ti] obeys henry's law at equilibrium, f [Ti] =1, and Then reduce the available formulas
Further, the mole fraction x [Ti] of [ Ti ] in Sn at the reaction equilibrium of the slag sample to be detected is an average value obtained from the mole fraction of [ Ti ] in Sn at the reaction equilibrium of the slag sample to be detected in five holes of the six-hole graphite crucible.
Further, the partial pressure p CO of CO and the standard atmospheric pressure p θ are 101325Pa.
Further, the analysis of the prepared slag sample to be detected and the reference slag sample is carried out by adopting an inductively coupled plasma atomic emission spectrometry.
Further, the six-hole graphite crucible is quenched by adopting an oil cooling mode.
Further, the air in the furnace tube is cleaned by N 2, and then the flow rate of CO is controlled to be 0.9-1.0L/min.
The method for measuring the activity of TiO 2 in blast furnace slag provided by the invention has the advantages that under T=1773K, metal Sn is used as a flux, C is used as a reducing agent, caF 2-TiO2 is used as reference slag, the activity of TiO 2 in the blast furnace slag is measured by adopting a reference slag method experiment, the measuring method is simple, the application range is wider, the accuracy of the measuring result of the method is high, and the method has important significance in realizing comprehensive utilization of titanium-containing blast furnace slag, enriching an activity database and the like.
Drawings
FIG. 1 is a flow chart of a method for determining the activity of TiO 2 in blast furnace slag according to an embodiment of the present invention;
Fig. 2 is a binary phase diagram of reference slag CaF 2-TiO2 in the method for determining the activity of TiO 2 in blast furnace slag according to the embodiment of the present invention.
Detailed Description
Referring to fig. 1, in the method for determining the activity of TiO 2 in blast furnace slag provided by the embodiment of the present invention, the activity of TiO 2 in blast furnace slag is determined by using a reference slag method, using CO as a shielding gas and Sn as a metal flux at t=1773k. The method specifically comprises the following steps:
step 1) putting equal mass metallic tin into each hole of the six-hole graphite crucible, putting a reference slag sample into one hole, and respectively putting to-be-detected slag samples with the same amount as the reference slag sample into the other five holes.
Wherein the reference slag is CaF 2-TiO2 slag system. As a specific embodiment of the invention, the reference slag comprises 30% of CaF 2 and 70% of TiO 2 in percentage by mass.
Wherein the slag to be detected is one of blast furnace type slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3-CaO and TiO 2-SiO2-Al2O3 -CaO-MgO slag system
And 2) when the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with the reference slag and the slag to be tested into a constant temperature zone in the furnace.
And 3) starting timing when the temperature of the tubular furnace sample rises to 1500+/-2 ℃, rapidly taking out the six-hole graphite crucible by using a graphite rod after heat preservation for 20-30 hours, and quenching to room temperature by using oil.
And 4) taking out the cooled reference slag sample and the slag sample to be detected from the six-hole graphite crucible respectively, and polishing and preparing each slag sample to obtain five slag samples to be detected and one reference slag sample.
And 5) respectively analyzing the five to-be-detected slag samples and one reference slag sample by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to respectively obtain the mass fraction of [ Ti ] in Sn of the five to-be-detected slag samples when the reaction is balanced and the mass fraction of [ Ti ] in Sn of the one reference slag sample when the reaction is balanced.
And 6) calculating the mole fraction x ref[Ti] of the Sn [ Ti ] in the reaction balance of the reference slag sample from the mass fraction of the Sn [ Ti ] in the reaction balance of the reference slag sample, calculating the mole fraction x [Ti] of the Sn [ Ti ] in the reaction balance of the five slag samples to be detected from the mass fraction of the Sn [ Ti ] in the reaction balance of the five slag samples to be detected, and then averaging the mole fractions of the Sn [ Ti ] in the reaction balance of the five slag samples to be detected.
Step 7) is represented by the formulaThe activity of TiO 2 in the slag sample to be detected can be calculated.
Wherein the formula isThe deduction method of (2) comprises the following steps:
The six-hole graphite crucible filled with the metal tin, the reference slag and the slag to be detected is placed in a high-temperature tube furnace, when the temperature is increased to 1500+/-2 ℃, the temperature is kept for 20-30 hours, and in the process, tiO 2 in the slag to be detected reacts as follows:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g) (1)
wherein,
The TiO 2 in the reference slag reacts as follows:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g) (3)
wherein,
In the method, in the process of the invention,And/>Respectively taking pure substances as the activities of TiO 2 in the slag to be detected and the reference slag in a standard state; a [Ti] and a ref[Ti] are respectively the activities of Ti in Sn when the reaction of the slag to be detected and the reference slag is balanced by taking the imaginary pure substances as standard states; p CO and p θ are the partial pressure of CO and the normal atmospheric pressure, respectively; since p CO＝pθ =101325 Pa and the reactions (1) and (3) of the TiO 2 in the slag to be measured and the reference slag are performed under the same condition, the activity standard states of the corresponding components are the same, and K 2＝K4 is needed, and the reactions include:
Since the concentration of Ti in Sn is low at the equilibrium of the reaction, the reaction is considered to obey henry's law, i.e., f [Ti] =1. Referring to fig. 2, when the temperature is t=1773K, in the CaF 2-TiO2 binary phase diagram, when the mass fraction of TiO 2 is greater than 60%, it is the saturation region of TiO 2, so when S (w (CaF 2) =30% and w (TiO 2) =70%) points are selected as the reference slag system, then Because of a [Ti]＝f[Ti]·x[Ti]、aref[Ti]＝f[Ti]·xref[Ti], formula (5) can be further simplified to formula (6):
The method for measuring the activity of TiO 2 in blast furnace slag provided by the invention is specifically described by the following examples.
Example 1
The embodiment of the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, wherein the selected reference slag is TiO 2：70(mass％)、CaF2: 30 (mass%).
The slag to be detected is selected as ：CaO：30(mass％)、Al2O3：15(mass％)、SiO2：22(mass％)、MgO：8(mass％)、TiO2：25(mass％).
At the beginning of the test, 5g of metal tin particles are put into each hole of the six-hole crucible, then 10g of reference slag sample is put into one hole, and 10g of slag sample to be tested is respectively put into the other five holes.
When the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with premelting slag into a constant temperature area in the furnace.
And after the temperature of the high-temperature tube furnace sample rises to 1500+/-2 ℃, keeping the temperature for 24 hours, rapidly taking out the six-hole graphite crucible by using a graphite rod and quenching by using oil.
And taking out the quenched sample, and polishing and preparing the slag sample respectively to obtain a reference slag sample and five slag samples to be detected.
And respectively analyzing the samples by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain the mass fractions of TiO 2 in metal phase Sn in one prepared reference slag sample and five to-be-detected slag samples.
The mole fraction x ref[Ti] of TiO 2 in the metal phase Sn in the reference slag sample can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the obtained reference slag sample, the mole fraction of [ Ti ] in Sn in the reaction balance of five slag samples to be detected can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the five slag samples to be detected, and then the mole fraction x [Ti] of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected can be calculated by averaging the mole fraction of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected.
Finally, by the formulaThe activity of TiO 2 in the slag to be detected provided in the embodiment can be calculated. In the embodiment, the mole fractions x ref[Ti] and x [Ti] of the slag sample [ Ti ] in Sn at the reaction equilibrium are calculated from the mass fraction of the [ Ti ] in Sn at the reaction equilibrium, and the activity/> of TiO 2 in the slag to be detected is calculatedPlease refer to table 1.
Example 2
The embodiment of the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps of: tiO 2：70(mass％)、CaF2: 30 (mass%);
The slag to be detected is selected as ：CaO：25(mass％)、Al2O3：20(mass％)、SiO2：25(mass％)、MgO：10(mass％)、TiO2：20(mass％).
At the beginning of the test, 5g of metal tin particles are put into each hole of the six-hole crucible, then 10g of reference slag sample is put into one hole, and 10g of slag sample to be tested is respectively put into the other five holes.
When the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with premelting slag into a constant temperature area in the furnace.
And after the temperature of the high-temperature tube furnace sample rises to 1500+/-2 ℃, keeping the temperature for 24 hours, rapidly taking out the six-hole graphite crucible by using a graphite rod and quenching by using oil.
And taking out the quenched sample, and polishing and preparing the slag sample respectively to obtain a reference slag sample and five slag samples to be detected.
And respectively analyzing the samples by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain the mass fractions of TiO 2 in metal phase Sn in one prepared reference slag sample and five to-be-detected slag samples.
The mole fraction x ref[Ti] of TiO 2 in the metal phase Sn in the reference slag sample can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the obtained reference slag sample, the mole fraction of [ Ti ] in Sn in the reaction balance of five slag samples to be detected can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the five slag samples to be detected, and then the mole fraction x [Ti] of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected can be calculated by averaging the mole fraction of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected.
Finally, by the formulaThe activity of TiO 2 in the slag to be detected provided in the embodiment can be calculated. In the embodiment, the mole fractions x ref[Ti] and x [Ti] of the slag sample [ Ti ] in Sn at the reaction equilibrium are calculated from the mass fraction of the [ Ti ] in Sn at the reaction equilibrium, and the activity/> of TiO 2 in the slag to be detected is calculatedPlease refer to table 1.
Example 3
The embodiment of the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps of: tiO 2：70(mass％)、CaF2: 30 (mass%);
The slag to be detected is selected as ：CaO：28(mass％)、Al2O3：15(mass％)、SiO2：24(mass％)、MgO：8(mass％)、TiO2：25(mass％).
At the beginning of the test, 5g of metal tin particles are put into each hole of the six-hole crucible, then 10g of reference slag sample is put into one hole, and 10g of slag sample to be tested is respectively put into the other five holes.
When the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with premelting slag into a constant temperature area in the furnace.
And after the temperature of the high-temperature tube furnace sample rises to 1500+/-2 ℃, keeping the temperature for 24 hours, rapidly taking out the six-hole graphite crucible by using a graphite rod and quenching by using oil.
And taking out the quenched sample, and polishing and preparing the slag sample respectively to obtain a reference slag sample and five slag samples to be detected.
And respectively analyzing the samples by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain the mass fractions of TiO 2 in metal phase Sn in one prepared reference slag sample and five to-be-detected slag samples.
The mole fraction x ref[Ti] of TiO 2 in the metal phase Sn in the reference slag sample can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the obtained reference slag sample, the mole fraction of [ Ti ] in Sn in the reaction balance of five slag samples to be detected can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the five slag samples to be detected, and then the mole fraction x [Ti] of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected can be calculated by averaging the mole fraction of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected.
Finally, by the formulaThe activity of TiO 2 in the slag to be detected provided in the embodiment can be calculated. In the embodiment, the mole fractions x ref[Ti] and x [Ti] of the slag sample [ Ti ] in Sn at the reaction equilibrium are calculated from the mass fraction of the [ Ti ] in Sn at the reaction equilibrium, and the activity/> of TiO 2 in the slag to be detected is calculatedPlease refer to table 1.
Example 4
The embodiment of the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps of: tiO 2：70(mass％)、CaF2: 30 (mass%);
The slag to be detected is selected as ：CaO：31(mass％)、Al2O3：15(mass％)、SiO2：24(mass％)、MgO：5(mass％)、TiO2：25(mass％).
At the beginning of the test, 5g of metal tin particles are put into each hole of the six-hole crucible, then 10g of reference slag sample is put into one hole, and 10g of slag sample to be tested is respectively put into the other five holes.
When the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with premelting slag into a constant temperature area in the furnace.
And after the temperature of the high-temperature tube furnace sample rises to 1500+/-2 ℃, keeping the temperature for 24 hours, rapidly taking out the six-hole graphite crucible by using a graphite rod and quenching by using oil.
And taking out the quenched sample, and polishing and preparing the slag sample respectively to obtain a reference slag sample and five slag samples to be detected.
And respectively analyzing the samples by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain the mass fractions of TiO 2 in metal phase Sn in one prepared reference slag sample and five to-be-detected slag samples.
The mole fraction x ref[Ti] of TiO 2 in the metal phase Sn in the reference slag sample can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the obtained reference slag sample, the mole fraction of [ Ti ] in Sn in the reaction balance of five slag samples to be detected can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the five slag samples to be detected, and then the mole fraction x [Ti] of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected can be calculated by averaging the mole fraction of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected.
Finally, by the formulaThe activity of TiO 2 in the slag to be detected provided in the embodiment can be calculated. In the embodiment, the mole fractions x ref[Ti] and x [Ti] of the slag sample [ Ti ] in Sn at the reaction equilibrium are calculated from the mass fraction of the [ Ti ] in Sn at the reaction equilibrium, and the activity/> of TiO 2 in the slag to be detected is calculatedPlease refer to table 1.
Example 5
The embodiment of the invention provides a method for measuring the activity of TiO 2 in blast furnace slag, which comprises the following steps of: tiO 2：70(mass％)、CaF2: 30 (mass%);
the slag to be detected is selected as ：CaO：35(mass％)、Al2O3：20(mass％)、SiO2：25(mass％)、MgO：15(mass％)、TiO2：5(mass％).
At the beginning of the test, 5g of metal tin particles are put into each hole of the six-hole crucible, then 10g of reference slag sample is put into one hole, and 10g of slag sample to be tested is respectively put into the other five holes.
When the sample temperature of the high-temperature tube furnace is raised to 700-800 ℃, firstly cleaning air in the furnace tube by using N 2, then introducing CO, controlling the flow rate of the CO to be 0.9-1.0L/min, and then slowly placing the six-hole graphite crucible filled with premelting slag into a constant temperature area in the furnace.
And after the temperature of the high-temperature tube furnace sample rises to 1500+/-2 ℃, keeping the temperature for 24 hours, rapidly taking out the six-hole graphite crucible by using a graphite rod and quenching by using oil.
And taking out the quenched sample, and polishing and preparing the slag sample respectively to obtain a reference slag sample and five slag samples to be detected.
And respectively analyzing the samples by using an inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain the mass fractions of TiO 2 in metal phase Sn in one prepared reference slag sample and five to-be-detected slag samples.
The mole fraction x ref[Ti] of TiO 2 in the metal phase Sn in the reference slag sample can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the obtained reference slag sample, the mole fraction of [ Ti ] in Sn in the reaction balance of five slag samples to be detected can be calculated from the mass fraction of TiO 2 in the metal phase Sn in the five slag samples to be detected, and then the mole fraction x [Ti] of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected can be calculated by averaging the mole fraction of [ Ti ] in Sn in the reaction balance of the five slag samples to be detected.
Finally, by the formulaThe activity of TiO 2 in the slag to be detected provided in the embodiment can be calculated. In the embodiment, the mole fractions x ref[Ti] and x [Ti] of the slag sample [ Ti ] in Sn at the reaction equilibrium are calculated from the mass fraction of the [ Ti ] in Sn at the reaction equilibrium, and the activity/> of TiO 2 in the slag to be detected is calculatedPlease refer to table 1.
Table 1.
The method for measuring the activity of TiO 2 in blast furnace slag provided by the invention has the advantages that under T=1773K, metal Sn is used as a flux, C is used as a reducing agent, caF 2-TiO2 is used as reference slag, the activity of TiO 2 in the blast furnace slag is measured by adopting a reference slag method experiment, the measuring method is simple, the application range is wider, the accuracy of the measuring result of the method is high, and the method has important significance in realizing comprehensive utilization of titanium-containing blast furnace slag, enriching an activity database and the like.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (9)
1. A method for determining the activity of TiO 2 in blast furnace slag, comprising the steps of:
Putting equal mass metal tin into each hole of a six-hole graphite crucible, putting a reference slag sample into one hole, and respectively putting to-be-detected slag samples with the same amount as the reference slag sample into the other five holes;
heating a tubular furnace sample to 700-800 ℃, removing air in a furnace tube, introducing CO, and then placing the six-hole graphite crucible into the tubular furnace;
heating the sample temperature of the tube furnace to 1500+/-2 ℃, preserving heat for 20-30 hours, and taking out the six-hole graphite crucible for quenching;
taking out the cooled reference slag sample and the slag sample to be detected, and polishing and preparing the slag sample respectively;
respectively analyzing the prepared slag sample to be detected and the reference slag sample to obtain the mass fraction of [ Ti ] in Sn when the reaction of the slag sample to be detected and the reference slag sample is balanced;
Respectively calculating x [Ti] and x ref[Ti] from mass fractions of [ Ti ] in Sn when the reaction balance of the slag sample to be detected and the reference slag sample is carried out;
From the formula Calculating to obtain the activity of TiO 2 in the slag sample to be detected;
Wherein x ref[Ti] is the mole fraction of [ Ti ] in Sn at the reference slag sample reaction equilibrium, and x [Ti] is the mole fraction of [ Ti ] in Sn at the slag sample reaction equilibrium to be detected;
Said formula The deduction method of (2) comprises the following steps:
The reaction of TiO 2 in the slag to be detected is as follows:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g)
The reaction of TiO 2 in the reference slag is as follows:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g)
Wherein, (TiO 2) and ref(TiO2) are the activities of TiO 2 in the slag to be detected and the reference slag taking pure substances as standard states respectively; ti and ref Ti are respectively the activities of Ti in Sn when the reaction of the slag to be detected and the reference slag is balanced by taking the imaginary pure substances as standard states; p CO and p θ are the partial pressure of CO and the normal atmospheric pressure, respectively;
Because the reaction of the slag to be detected and the reference slag is carried out under the same condition, when the activity standard states of the corresponding components are the same, K 2＝K4 is as follows:
since [ Ti ] =f [Ti]·x[Ti]、ref[Ti]＝f[Ti]·xref [ Ti ], the reaction is balanced by henry's law, f [Ti] =1, and Then reduce the available formulas
2. The method for determining the activity of TiO 2 in blast furnace slag according to claim 1, wherein the reference slag is CaF 2-TiO2 slag system.
3. The method for determining the activity of TiO 2 in blast furnace slag according to claim 2, wherein the reference slag is 30% CaF 2 and 70% TiO 2 by mass.
4. The method for measuring the activity of TiO 2 in blast furnace slag according to claim 1, wherein the slag to be measured is one of blast furnace slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3-CaO and TiO 2-SiO2-Al2O3 -CaO-MgO slag system.
5. The method for measuring the activity of TiO 2 in blast furnace slag according to claim 1, wherein the mole fraction [ Ti ] of Sn at the reaction equilibrium of the slag sample to be measured is an average value obtained from the mole fraction of [ Ti ] of Sn at the reaction equilibrium of the slag sample to be measured in five holes of a six-hole graphite crucible.
6. The method for determining the activity of TiO 2 in blast furnace slag according to claim 1, wherein the partial pressure CO of CO and the normal atmospheric pressure p θ are 101325Pa.
7. The method for determining activity of TiO 2 in blast furnace slag according to claim 1, wherein the analysis of the prepared slag sample to be detected and the reference slag sample is performed by inductively coupled plasma atomic emission spectrometry.
8. The method for measuring the activity of TiO 2 in blast furnace slag according to claim 1, wherein the six-hole graphite crucible is quenched by oil cooling.
9. The method for measuring activity of TiO 2 in blast furnace slag according to claim 1, wherein the air in the cleaning furnace tube is cleaned by N 2, and then the flow rate of CO is controlled to be 0.9-1.0L/min.
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