CN114486858A - Determination of TiO in blast furnace type slag2Method of activity - Google Patents
Determination of TiO in blast furnace type slag2Method of activity Download PDFInfo
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- CN114486858A CN114486858A CN202210030798.9A CN202210030798A CN114486858A CN 114486858 A CN114486858 A CN 114486858A CN 202210030798 A CN202210030798 A CN 202210030798A CN 114486858 A CN114486858 A CN 114486858A
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- 230000000694 effects Effects 0.000 title claims abstract description 47
- 239000002893 slag Substances 0.000 claims abstract description 252
- 238000000034 method Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 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
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- 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
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 74
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 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 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 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
- 238000009795 derivation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 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
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910008839 Sn—Ti Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 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
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006467 substitution reaction 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
Abstract
The invention provides a method for measuring TiO in blast furnace type slag2A method of activity, comprising the steps of: adding metallic tin, a reference slag sample and a slag sample to be detected into a six-hole graphite crucible; putting the six-hole graphite crucible into a tube furnace; heating the tubular furnace sample to 1500 +/-2 ℃, preserving the temperature for 20-30h, taking out the six-hole graphite crucible, and quenching; taking out the cooled reference slag sample and the cooled slag sample to be measured, and respectively polishing and sample preparation the slag sample; respectively analyzing [ Ti ] in Sn during reaction balance for the prepared slag sample to be detected and the reference slag sample]Mass fraction of (a); respectively calculate to obtain x[Ti]And xref[Ti](ii) a By the formula
Calculating to obtain TiO in the slag sample to be measured2Activity of (c). The invention provides a method for measuring TiO in blast furnace type slag2The activity method is simple in determination method and high in determination accuracy.
Description
Technical Field
The invention relates to the technical field of physicochemical tests, in particular to a method for measuring TiO in blast furnace type slag2Method of activity.
Background
In the blast furnace smelting process, titanium is more difficult to reduce than iron, so that almost all titanium enters a slag phase to form TiO2The titanium-containing blast furnace slag with the mass fraction of more than 20 percent has important significance for realizing the comprehensive utilization of the titanium-containing blast furnace slag, measuring the activity of the titanium-containing blast furnace slag system component, enriching the activity database and the like.
How to measure the activity of the component is an important direction for studying the thermodynamic performance of the component, but the measurement of the activity of the component is still very difficult at present due to the complexity of high temperature experiments and the precision of experimental data. The current methods for measuring the activity of components in blast furnace slag mainly comprise a chemical equilibrium method, an electromotive force method, a steam pressure method, a distribution equilibrium method, a G-D formula calculation method, a partial molar thermodynamic function calculation method and the like. Due to the influence of the complexity of high-temperature experiments and the precision of experimental data, thermodynamic data are often required to be quoted when the component activity is measured in experiments 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 activity calculation method and the like, so that the inaccuracy of the experimental data is easily caused.
Therefore, there is a need for an effective method for increasing TiO in blast furnace slag2The method for measuring the accuracy of the experimental data by the activity avoids the measurement error easily caused by the fact that thermodynamic data need to be quoted by other methods.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for measuring TiO in blast furnace type slag, which has simple measuring method and high measuring accuracy2Method of activity.
In order to solve the technical problem, the invention provides a method for measuring TiO in blast furnace type slag2An activity method comprising the steps of:
putting equal-mass metal tin into each hole of the six-hole graphite crucible, putting a reference slag sample into one hole, and putting the slag samples to be detected into the other five holes respectively, wherein the amount of the slag samples to be detected is equal to that of the reference slag sample;
raising the temperature of the tubular furnace sample to 700-800 ℃, removing air in a furnace tube, introducing CO, and putting the six-hole graphite crucible into the tubular furnace;
heating the tubular furnace sample to 1500 +/-2 ℃, preserving the temperature for 20-30h, taking out the six-hole graphite crucible, and quenching;
taking out the cooled reference slag sample and the cooled slag sample to be measured, and respectively polishing and sample preparation the slag sample;
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;
in Sn [ Ti ] when the reaction of the slag sample to be measured and the reference slag sample is balanced]Respectively calculating the mass fraction of the obtained x[Ti]And xref[Ti]；
By the formula
Calculating to obtain TiO in the slag sample to be measured2Activity of (d);
wherein x isref[Ti]In Sn for reference slag sample reaction equilibrium]Mole fraction of (a), x[Ti]In Sn [ Ti ] for reaction equilibrium of slag sample to be measured]Mole fraction of (c).
Further, the reference slag is CaF2-TiO2And (4) slag system.
Further, the reference slag comprises CaF (calcium fluoride) in percentage by mass 230% of TiO2The content was 70%.
Further, the slag to be detected is blast furnace type slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3CaO and TiO2-SiO2-Al2O3-one of CaO-MgO slag systems.
Further, the formula
The derivation method comprises the following steps:
TiO in the slag to be detected2The reaction of (a) is:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g)
TiO in the reference slag2The reaction of (a) is:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g)
in the formula (I), the compound is shown in the specification,
and
respectively TiO in the slag to be measured and the reference slag which take pure substances as standard states2Activity of (d); a is[Ti]And aref[Ti]Respectively taking the hypothetical pure substances as standard states, and the activity of Ti in Sn when the reaction of the slag to be measured and the reference slag is balanced; p is a radical ofCOAnd pθPartial pressure of CO and standard 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 is2＝K4And then:
due to a[Ti]＝f[Ti]·x[Ti]、aref[Ti]＝f[Ti]·xref[Ti]Reaction ofEquilibrium obeys Henry's law, then[Ti]1, and
then simplify the available formula
Further, the [ Ti ] in Sn when the reaction of the slag sample to be detected is balanced]Mole fraction x of[Ti]Is the [ Ti ] in Sn when the reaction of a slag sample to be measured in five holes of a six-hole graphite crucible is balanced]Average value obtained from the mole fraction of (c).
Further, the partial pressure p of COCOAnd standard atmospheric pressure pθAre all 101325 Pa.
Further, the step of respectively analyzing the prepared slag sample to be detected and the reference slag sample is to analyze by adopting an inductively coupled plasma atomic emission spectrometry.
Further, the quenching of the six-hole graphite crucible is carried out in an oil cooling mode.
Further, the air in the furnace tube is removed by N2Air in the furnace tube is cleaned, and then the flow of the introduced CO is controlled to be 0.9-1.0L/min.
The invention provides a method for measuring TiO in blast furnace type slag2The method of activity, under T1773K, using metal Sn as flux, C as reducer, CaF2-TiO2For reference slag, TiO in blast furnace type slag is experimentally measured by adopting a reference slag method2The activity of the method is simple, has a wide application range, has high accuracy of the measured result, and has important significance for realizing comprehensive utilization of the titanium-containing blast furnace slag, enriching an activity database and the like.
Drawings
FIG. 1 is a diagram for measuring TiO content in blast furnace slag according to an embodiment of the present invention2A process flow diagram of an activity;
FIG. 2 is a diagram illustrating the determination of TiO in blast furnace slag according to an embodiment of the present invention2Reference slag CaF in activity method2-TiO2A binary phase diagram.
Detailed Description
Referring to fig. 1, the embodiment of the invention provides a method for measuring TiO in blast furnace type slag2The activity method is to measure TiO in blast furnace slag by using a reference slag method under the conditions that T is 1773K, CO is used as protective gas, Sn is used as metal flux2Activity of (c). The method specifically comprises the following steps:
step 1) putting equal-mass metal tin into each hole of a six-hole graphite crucible, putting a reference slag sample into one hole, and putting a to-be-detected slag sample which is equal to the reference slag sample into the other five holes respectively.
Wherein the reference slag is CaF2-TiO2And (4) slag system. As a specific implementation mode of the invention, the CaF in the reference slag is calculated by mass percent 230% of TiO2The content was 70%.
Wherein, the slag to be measured is blast furnace type slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3CaO and TiO2-SiO2-Al2O3One of-CaO-MgO slag systems
Step 2) when the temperature of the high-temperature tubular furnace sample rises to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO to be 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the reference slag and the slag to be detected into a constant temperature area in the furnace.
And 3) starting timing when the temperature of the tubular furnace sample rises to 1500 +/-2 ℃, quickly taking out the six-hole graphite crucible by using a graphite rod after heat preservation is carried out for 20-30h, and quenching to room temperature by using oil.
And 4) taking the cooled reference slag sample and the cooled slag sample to be detected out of the six-hole graphite crucible respectively, and polishing and sample preparation are carried out on each slag sample respectively to obtain five slag samples to be detected and one reference slag sample.
And 5) analyzing the five prepared slag samples to be detected and one reference slag sample by using inductively coupled plasma atomic emission spectrometry (ICP-AES) respectively to obtain the mass fraction of [ Ti ] in Sn of the five slag samples to be detected in reaction equilibrium and the mass fraction of [ Ti ] in Sn of the reference slag sample in reaction equilibrium respectively.
Step 6) reaction equilibrium of the reference slag sample in Sn [ Ti]The mass fraction of the (B) can be calculated to obtain [ Ti ] in Sn of a reference slag sample during reaction equilibrium]Mole fraction x ofref[Ti]In the Sn, [ Ti ] in the five slag samples to be measured during reaction equilibrium]The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined, and the five slag samples to be measured are in Sn [ Ti ] during reaction equilibrium]The average value of the mole fractions is obtained, and the Ti in Sn is obtained when the slag sample to be measured is in reaction equilibrium]Mole fraction x of[Ti]。
Step 7) is represented by the formula
Can calculate to obtain TiO in the slag sample to be measured2Activity of (c).
Wherein, the formula
The derivation method comprises the following steps:
placing the six-hole graphite crucible filled with the metallic tin, the reference slag and the slag to be detected in a high-temperature tube furnace, and when the temperature is raised to 1500 +/-2 ℃, preserving the heat for 20-30h, wherein TiO in the slag to be detected2The following reactions occur:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g) (1)
wherein the content of the first and second substances,
TiO in reference slag2The following reactions occur:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g) (3)
wherein the content of the first and second substances,
in the formula (I), the compound is shown in the specification,
and
respectively TiO in the slag to be measured and the reference slag which take pure substances as standard states2Activity of (d); a is[Ti]And aref[Ti]Respectively taking the hypothetical pure substances as standard states, and the activity of Ti in Sn when the reaction of the slag to be measured and the reference slag is balanced; p is a radical ofCOAnd pθPartial pressure of CO and standard atmospheric pressure respectively; due to pCO＝pθ101325Pa, and the above TiO2The reactions (1) and (3) in the slag to be measured and the reference slag are carried out under the same condition, the activity standard states of the corresponding components are the same, and K must be present2＝K4Then, there are:
the reaction is balanced due to [ Ti ] in Sn]Is low, the reaction can be considered to obey Henry's law, i.e. f[Ti]1. Referring to fig. 2, when the temperature is T1773K, in CaF2-TiO2In the binary phase diagram, when TiO is2When the mass fraction is more than 60 percent, the material is TiO2The saturation region of (1), therefore, when S (w (CaF) is selected2) 30% and w (TiO)2) 70%) as reference slag system, then
Due to a[Ti]＝f[Ti]·x[Ti]、aref[Ti]＝f[Ti]·xref[Ti]Then, equation (5) can be further simplified to equation (6):
the invention is provided by the following examplesTo determine TiO in blast furnace type slag2The activity method is specifically explained.
Example 1
The embodiment of the invention provides a method for measuring TiO in blast furnace type slag2The activity method adopts TiO as reference slag2：70(mass％)、CaF2：30(mass％)。
The selected to-be-detected slag comprises: CaO: 30 (mass%), Al2O3：15(mass％)、SiO2：22(mass％)、MgO：8(mass％)、TiO2：25(mass％)。
When the test is started, 5g of metallic 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 temperature of the high-temperature tubular furnace sample rises to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO at 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the pre-melted slag into a constant temperature area in the furnace.
And (3) when the temperature of the high-temperature tubular furnace sample rises to 1500 +/-2 ℃, keeping the temperature for 24 hours, quickly taking out the six-hole graphite crucible by using a graphite rod, and quenching by using oil.
And taking out the quenched sample, and respectively polishing and preparing the slag sample to obtain one reference slag sample and five to-be-detected slag samples.
Respectively analyzing the samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain one reference slag sample and five slag samples to be detected2Mass fraction of (c).
TiO in metal phase Sn in the obtained reference slag sample2The mass fraction of the Sn-Ti alloy can be calculated to obtain the TiO in the metal phase Sn in the reference slag sample2Mole fraction x ofref[Ti]And obtaining the TiO in the metal phase Sn in the five slag samples to be detected2The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined by five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The average value of the mole fraction is calculated to obtain the slag sample to be measuredProduct is [ Ti ] in Sn at reaction equilibrium]Mole fraction x of[Ti]。
Finally, the formula
Namely, the TiO in the slag to be measured provided by the embodiment can be calculated2Activity of (c). In this example, the [ Ti ] in Sn is present in the slag sample at the reaction equilibrium]The slag sample calculated by the mass fraction of (A) is in the Sn [ Ti ] during the reaction equilibrium]Mole fraction x ofref[Ti]And x[Ti]And calculating to obtain TiO in the slag to be measured2Activity of
Please see table 1.
Example 2
The embodiment of the invention provides a method for measuring TiO in blast furnace type slag2The activity method comprises the following steps of: TiO 22：70(mass％)、CaF2：30(mass％)；
The selected to-be-detected slag comprises: CaO: 25 (mass%), Al2O3：20(mass％)、SiO2：25(mass％)、MgO：10(mass％)、TiO2：20(mass％)。
When the test is started, 5g of metallic 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 temperature of the high-temperature tube furnace sample rises to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO at 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the pre-melted slag into a constant temperature area in the furnace.
And (3) when the temperature of the high-temperature tubular furnace sample rises to 1500 +/-2 ℃, keeping the temperature for 24 hours, quickly taking out the six-hole graphite crucible by using a graphite rod, and quenching by using oil.
And taking out the quenched sample, and respectively polishing and preparing the slag sample to obtain one reference slag sample and five to-be-detected slag samples.
Respectively using inductively coupled plasma atomic emission spectrometry (ICP-AES) is used for analyzing the sample, so that one reference slag sample and five slag samples to be detected can be obtained2Mass fraction of (c).
TiO in metal phase Sn in the obtained reference slag sample2The mass fraction of the Sn-Ti alloy can be calculated to obtain the TiO in the metal phase Sn in the reference slag sample2Mole fraction x ofref[Ti]And obtaining the TiO in the metal phase Sn in the five slag samples to be detected2The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined by five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The average value of the mole fractions is obtained, and the [ Ti ] in Sn is obtained when the reaction of the slag sample to be measured is balanced]Mole fraction x of[Ti]。
Finally, the formula
Namely, the TiO in the slag to be measured provided by the embodiment can be calculated2Activity of (c). In this example, the [ Ti ] in Sn is present in the slag sample at the reaction equilibrium]The slag sample calculated by the mass fraction of (A) is in the Sn [ Ti ] during the reaction equilibrium]Mole fraction x ofref[Ti]And x[Ti]And calculating to obtain TiO in the slag to be measured2Activity of
See table 1.
Example 3
The embodiment of the invention provides a method for measuring TiO in blast furnace type slag2The activity method comprises the following steps of: TiO 22：70(mass％)、CaF2：30(mass％)；
The selected residues to be detected are as follows: CaO: 28 (mass%), Al2O3：15(mass％)、SiO2：24(mass％)、MgO：8(mass％)、TiO2：25(mass％)。
When the test is started, 5g of metallic 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.
Waiting high temperature tube furnace sampleWhen the temperature is raised to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO at 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the pre-melted slag into a constant temperature area in the furnace.
And (3) when the temperature of the high-temperature tubular furnace sample rises to 1500 +/-2 ℃, keeping the temperature for 24 hours, quickly taking out the six-hole graphite crucible by using a graphite rod, and quenching by using oil.
And taking out the quenched sample, and respectively polishing and preparing the slag sample to obtain one reference slag sample and five to-be-detected slag samples.
Respectively analyzing the samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain one reference slag sample and five slag samples to be detected2The mass fraction of (c).
TiO in metal phase Sn in the obtained reference slag sample2The mass fraction of the Sn-Ti alloy can be calculated to obtain the TiO in the metal phase Sn in the reference slag sample2Mole fraction x ofref[Ti]And obtaining the TiO in the metal phase Sn in the five slag samples to be detected2The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined by five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The average value of the mole fractions is obtained, and the [ Ti ] in Sn is obtained when the reaction of the slag sample to be measured is balanced]Mole fraction x of[Ti]。
Finally, the formula
Namely, the TiO in the slag to be measured provided by the embodiment can be calculated2Activity of (c). In this example, the [ Ti ] in Sn is present in the slag sample at the reaction equilibrium]The slag sample calculated by the mass fraction of (A) is in the Sn [ Ti ] during the reaction equilibrium]Mole fraction x ofref[Ti]And x[Ti]And calculating to obtain TiO in the slag to be measured2Activity of
See table 1.
Example 4
The inventionThe embodiment provides a method for measuring TiO in blast furnace type slag2The activity method comprises the following steps of: TiO 22：70(mass％)、CaF2：30(mass％)；
The selected to-be-detected slag comprises: CaO: 31 (mass%), Al2O3：15(mass％)、SiO2：24(mass％)、MgO：5(mass％)、TiO2：25(mass％)。
When the test is started, 5g of metallic tin particles are placed in each hole of the six-hole crucible, then 10g of reference slag sample is placed in one hole, and 10g of slag sample to be tested is placed in the other five holes respectively.
When the temperature of the high-temperature tubular furnace sample rises to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO at 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the pre-melted slag into a constant temperature area in the furnace.
And (3) when the temperature of the high-temperature tubular furnace sample rises to 1500 +/-2 ℃, keeping the temperature for 24 hours, quickly taking out the six-hole graphite crucible by using a graphite rod, and quenching by using oil.
And taking out the quenched sample, and respectively polishing and preparing the slag sample to obtain one reference slag sample and five to-be-detected slag samples.
Respectively analyzing the samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain one reference slag sample and five slag samples to be detected2Mass fraction of (c).
TiO in metal phase Sn in the obtained reference slag sample2The mass fraction of the Sn-Ti alloy can be calculated to obtain the TiO in the metal phase Sn in the reference slag sample2Mole fraction x ofref[Ti]And obtaining the TiO in the metal phase Sn in the five slag samples to be detected2The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined by five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The average value of the mole fractions is obtained, and the [ Ti ] in Sn is obtained when the reaction of the slag sample to be measured is balanced]Mole fraction x of[Ti]。
Finally, the formula
Namely, the TiO in the slag to be measured provided by the embodiment can be calculated2Activity of (c). In this example, the [ Ti ] in Sn is present in the slag sample at the reaction equilibrium]The slag sample calculated by the mass fraction of (A) is in the Sn [ Ti ] during the reaction equilibrium]Mole fraction x ofref[Ti]And x[Ti]And calculating to obtain TiO in the slag to be measured2Activity of
See table 1.
Example 5
The embodiment of the invention provides a method for measuring TiO in blast furnace type slag2The activity method comprises the following steps of: TiO 22：70(mass％)、CaF2：30(mass％)；
The selected to-be-detected slag comprises: CaO: 35 (mass%), Al2O3：20(mass％)、SiO2：25(mass％)、MgO：15(mass％)、TiO2：5(mass％)。
When the test is started, 5g of metallic 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 temperature of the high-temperature tubular furnace sample rises to 700-800 ℃, N is firstly used2Cleaning air in the furnace tube, introducing CO, controlling the flow of the CO at 0.9-1.0L/min, and slowly placing the six-hole graphite crucible filled with the pre-melted slag into a constant temperature area in the furnace.
And (3) when the temperature of the high-temperature tubular furnace sample rises to 1500 +/-2 ℃, keeping the temperature for 24 hours, quickly taking out the six-hole graphite crucible by using a graphite rod, and quenching by using oil.
And taking out the quenched sample, and respectively polishing and preparing the slag sample to obtain one reference slag sample and five to-be-detected slag samples.
Respectively analyzing the samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) to obtain one reference slag sample and five slag samples to be detected2Mass fraction of (c).
TiO in metal phase Sn in the obtained reference slag sample2The mass fraction of the Sn-Ti alloy can be calculated to obtain the TiO in the metal phase Sn in the reference slag sample2Mole fraction x ofref[Ti]And obtaining the TiO in the metal phase Sn in the five slag samples to be detected2The mass fraction of the (A) can be respectively calculated to obtain five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The mole fraction of the (C) is then determined by five slag samples to be measured in Sn [ Ti ] during reaction equilibrium]The average value of the mole fractions is obtained, and the [ Ti ] in Sn is obtained when the reaction of the slag sample to be measured is balanced]Mole fraction x of[Ti]。
Finally, the formula
Namely, the TiO in the slag to be measured provided by the embodiment can be calculated2Activity of (c). In this example, the [ Ti ] in Sn is present in the slag sample at the reaction equilibrium]The slag sample calculated by the mass fraction of (A) is in the Sn [ Ti ] during the reaction equilibrium]Mole fraction x ofref[Ti]And x[Ti]And calculating to obtain TiO in the slag to be measured2Activity of
See table 1.
Table 1.
The invention provides a method for measuring TiO in blast furnace type slag2The method of activity, under T1773K, using metal Sn as flux, C as reducer, CaF2-TiO2For reference slag, TiO in blast furnace type slag is experimentally measured by adopting a reference slag method2The activity determination method is simple, has a wide application range, has high accuracy of the determination result, and has important significance in realizing comprehensive utilization of the titanium-containing blast furnace slag, enriching an activity database and the like.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. Determination of TiO in blast furnace type slag2An activity method, comprising the steps of:
putting equal-mass metal tin into each hole of the six-hole graphite crucible, putting a reference slag sample into one hole, and putting the slag samples to be detected into the other five holes respectively, wherein the amount of the slag samples to be detected is equal to that of the reference slag sample;
raising the temperature of the tubular furnace sample to 700-800 ℃, removing air in a furnace tube, introducing CO, and putting the six-hole graphite crucible into the tubular furnace;
heating the tubular furnace sample to 1500 +/-2 ℃, preserving the temperature for 20-30h, taking out the six-hole graphite crucible, and quenching;
taking out the cooled reference slag sample and the cooled slag sample to be measured, and respectively polishing and sample preparation the slag sample;
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;
in Sn [ Ti ] when the reaction of the slag sample to be measured and the reference slag sample is balanced]Respectively calculating the mass fraction of the obtained x[Ti]And xref[Ti]；
By the formula
Calculating to obtain TiO in the slag sample to be measured2Activity of (d);
wherein x isref[Ti]In Sn for reference slag sample reaction equilibrium]Mole fraction of (a), x[Ti]In Sn [ Ti ] for reaction equilibrium of slag sample to be measured]Mole fraction of (c).
2. The method according to claim 1 for determining TiO in blast furnace slag2An activity method, characterized in that the reference slag is CaF2-TiO2And (4) slag system.
3. The method according to claim 2, wherein the TiO content in the blast furnace slag is measured2An activity method, characterized in that the reference slag, in mass percent, CaF230% of TiO2The content was 70%.
4. The method according to claim 1 for determining TiO in blast furnace slag2The activity method is characterized in that the slag to be measured is blast furnace type slag TiO2-MgO-Al2O3、TiO2-SiO2-Al2O3、TiO2-CaO-SiO2、TiO2-MgO-SiO2、TiO2-SiO2-Al2O3CaO and TiO2-SiO2-Al2O3-one of CaO-MgO slag systems.
5. The method according to claim 1 for determining TiO in blast furnace slag2Method of activity, characterized in that said formula
The derivation method comprises the following steps:
TiO in the slag to be detected2The reaction of (a) is:
(TiO2)mea.+C(graphite)＝[Ti]Sn+CO(g)
TiO in the reference slag2The reaction of (a) is:
(TiO2)ref.+C(graphite)＝[Ti]Sn+CO(g)
in the formula (TiO)2) Andref(TiO2) Respectively TiO in the slag to be measured and the reference slag which take pure substances as standard states2Activity of (d); [ Ti ]]Andref[Ti]respectively taking the hypothetical pure substances as standard states, and the activity of Ti in Sn when the reaction of the slag to be measured and the reference slag is balanced; p is a radical ofCOAnd pθPartial pressure of CO and standard 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 is2＝K4And then:
due to [ Ti]＝f[Ti]·x[Ti]、ref[Ti]＝f[Ti]·xref[Ti]When the reaction is balanced, obeying Henry's law, then[Ti]1, andref(TiO2) 1, then the simplified formula
6. The method according to claim 5, wherein the TiO content in the blast furnace slag is measured2The activity method is characterized in that [ Ti ] in Sn during reaction equilibrium of the slag sample to be detected]Mole fraction of [ Ti ]]Is the [ Ti ] in Sn when the reaction of a slag sample to be measured in five holes of a six-hole graphite crucible is balanced]Average value obtained from the mole fraction of (c).
7. The method according to claim 5, wherein the TiO content in the blast furnace slag is measured2Method of activity, characterized in that the partial pressure of CO and the standard atmospheric pressure pθAre all 101325 Pa.
8. The method according to claim 1 for determining TiO in blast furnace slag2The activity method is characterized in that the prepared slag sample to be measured is subjected to activity matchingAnd the respective analysis of the sample and the reference slag sample is carried out by adopting an inductively coupled plasma atomic emission spectrometry.
9. The method according to claim 1 for determining TiO in blast furnace slag2The activity method is characterized in that the quenching of the six-hole graphite crucible is carried out in an oil cooling mode.
10. The method according to claim 1 for determining TiO in blast furnace slag2The method of activity is characterized in that the air in the furnace tube is cleaned by N2Air in the furnace tube is cleaned, and then the flow of the introduced CO is controlled to be 0.9-1.0L/min.
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