CN108226373A - The detection method of impurity content in a kind of titanium sponge - Google Patents
The detection method of impurity content in a kind of titanium sponge Download PDFInfo
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- CN108226373A CN108226373A CN201711337745.7A CN201711337745A CN108226373A CN 108226373 A CN108226373 A CN 108226373A CN 201711337745 A CN201711337745 A CN 201711337745A CN 108226373 A CN108226373 A CN 108226373A
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- titanium sponge
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
Abstract
The present invention provides a kind of detection method of impurity content in titanium sponge, comprises the steps of：1) titanium sponge is weighed, records its initial mass；2) it dries titanium sponge and removes TiCl4, the titanium sponge after drying is weighed and recorded；3) ethyl alcohol and catalyst are added in, is heated to predetermined temperature, measures the amount for generating gas；4) acid indicator is added in, with acidometric titration to titration end-point；5) insoluble substance is filtered to remove, and solution is divided into three parts；6) metal indicator is added in, and titration end-point is titrated to using EDTA to first part of solution；7) mercuric nitrate is added in into second part of solution to be titrated；8) amount of whole Ti elements in third part solution is measured；9) amount of each impurity is calculated according to related substances consumption.The required detection device of the present invention is simple, and detecting step is simple, and the content of all substances can be obtained by measuring the content of Mg, Cl, Ti.
Description
Technical field
The present invention relates to the assay method of impurity content in titanium sponge, applied to four chlorination of magnesiothermic reduction in small-sized atmosphere furnace
Product detection obtained by titanium.
Background technology
At present, the commercial run of Titanium production is Kroll methods.In production process, titaniferous ore (rutile, high titanium slag
Deng) pass through the obtained TiCl of chlorination (shaft chlorination, fused salt chlorimation, fluidizing chlorination etc.)4, magnesium reduction process is reused by TiCl4Turn
Elemental form is turned to, reduzate is then handled by the method for vacuum distillation, removes volatile impurity, obtains titanium sponge production
Product.The method prepares titanium sponge technique and belongs to batch production, fail realize production serialization, production time-consuming, overall process from
TiO2Chlorination start to produce titanium sponge need 17 days, production cost is very high.
In view of the above problems, have investigated magnesiothermic reduction-vacuum distillation integration apparatus.And existing titanium sponge impurity inspection
For survey technology for the product obtained with magnesiothermic reduction-vacuum distillation integral method, detection method is complicated for operation cumbersome,
Analyze speed is low, and sensitivity is low.
Invention content
For this purpose, the present invention provides a kind of detection method of impurity content in titanium sponge, this method can simply measure body
The content of each element in system, by the content that can be calculated each impurity.
According to an aspect of the present invention, a kind of detection method of impurity content in titanium sponge is provided, this method includes following
Step：
1) titanium sponge is weighed, records its initial mass；
2) titanium sponge is dried to removing TiCl with filter paper4Until, the titanium sponge after drying is weighed, records its quality,
Mass Calculation based on initial mass and after drying goes out TiCl4Quality；
3) ethyl alcohol and catalyst are added in into the sample of drying, and is heated to predetermined temperature, dissolves sample, measures and generates
The amount of gas calculates the mole of metal Mg according to the amount of gas；
4) acid indicator is added in into the solution of step 3), with dilute H2SO4Titration end-point is titrated to, according to the dilute of consumption
H2SO4Molar amount calculate MgO mole；
5) filtration step 4) obtained by solution, remove insoluble substance, and solution is divided into three parts；
6) pH value of first part of solution is adjusted to predetermined value, adds in metal indicator later, and utilize ethylenediamine tetraacetic
Two sodium solution of acetic acid carries out being titrated to titration end-point, records the consumption of disodium ethylene diamine tetra-acetic acid solution and according to ethylenediamine
The mole of MgO that the mole and step 4) for the metal Mg that the consumption of tetraacethyl disodium solution, step 3) calculate calculate
To calculate MgCl2Mole；
7) mercuric nitrate is added in into second part of solution to be titrated, measure the quality of precipitation to calculate mole of Cl ions
Amount；
8) mole of whole Ti ions in third part solution from step 5) is measured；
9) TiCl in sample is calculated2And TiCl3Mole and mass fraction.
According to one embodiment of present invention, TiCl in step 9)2And TiCl3Mole be to be obtained according in step 1)
TiCl4Quality, the MgCl that obtains in step 6)2Mole, the mole and step of the Cl ions that obtain in step 7)
It is rapid 8) in the mole of Ti ions that obtains calculate.
According to one embodiment of present invention, catalyst includes iodine or mercury chloride, preferably iodine in step 3).Heating temperature
At 60 DEG C or more.
According to one embodiment of present invention, the volume of generation gas is measured in step 3) using drainage.
According to one embodiment of present invention, acid indicator is purple reindeer moss in step 4).
According to one embodiment of present invention, the predetermined value of pH value is 10 in step 6).
According to one embodiment of present invention, metal indicator is eriochrome black T in step 6).
According to one embodiment of present invention, in step 8) using inductive coupling plasma emission spectrograph measure Ti from
The amount of son.
According to one embodiment of present invention, step 3) and acid used in step 4) are dilute sulfuric acid.
According to one embodiment of present invention, titanium sponge is prepared by magnesiothermic reduction-vacuum distillation integral method
It arrives.
By using the above method of the present invention, following multiple beneficial effect can be obtained：
(1) the required detection device of the present invention and step are simple, and all substances can be obtained by measuring the amount of Mg, Cl, Ti
Content；
(2) testing principle of the invention is simple, does not need to be measured specific to low valence titanium ion, only need to pass through measurement
Full Ti and full Cl, you can to calculate Ti2+、Ti3+Content；
(3) by being detached to refining titanium products, and the directly technological means of detection and indirect analysis is combined, to refining titanium production
The Ti directly detected is difficult in object2+、Ti3+Carry out quantitative detecting analysis.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer with reference to specific embodiments to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and do not have to
It is of the invention in limiting.
The titanium sponge that the method for the present invention is prepared for measure by magnesiothermic reduction-vacuum distillation integral method.
Magnesiothermic reduction-vacuum distillation integration refining titanium technological principle is specific as follows：With magnesium metal and TiCl4For raw material, in vacuum condition
Lower TiCl4750~850 DEG C of gasifications are heated to, by TiCl4Steam is passed through in molten metal magnesium, is improved and reacted by combustion system
Indoor temperature；Start titanium tetrachloride heating tank, titanium tetrachloride gases are sent into molten metal magnesium, magnesium metal and four chlorinations
Reduction reaction occurs for titanium, generates Titanium and magnesium chloride, and Sponge Titanium is obtained through cooling.Ingredient is answered in the Sponge Titanium
It is miscellaneous, except containing TiCl4Outside, also containing Ti, TiCl2、TiCl3、TiO2、Mg、MgCl2、 MgO。
Method provided by the invention can quantify detect in above-mentioned titanium sponge impurity (impurity include TiCl2、TiCl3、
TiCl4、Mg、MgCl2、MgO).The detection method of the present invention is detailed below.For ease of description, by TiCl2、TiCl3、
Mg、MgCl2, MgO the amount of substance represented respectively by a, b, c, d, e.The content that each amount can determine each impurity composition is obtained.
First, titanium sponge is weighed, records its initial mass M1.
Due to TiCl4It is at normal temperatures liquid, therefore titanium sponge is dried with filter paper, weighs, record its mass M 2, Ke Yiji
Calculate TiCl4Quality is M1-M2.
Titanium sponge after drying is placed in container, adding in ethyl alcohol and catalyst at 60 DEG C or more makes its dissolving, metal Mg
Hydrogen is generated with ethanol synthesis, with the volume of drainage measure hydrogen, the ratio between amount of substance of hydrogen and magnesium metal is 1, by hydrogen
Gas gauge calculates c moles of the amount of the substance of magnesium metal.
It is titrated again with dilute sulfuric acid, so as to dissolve MgO.By the use of purple reindeer moss as acid indicator, when MgO all dissolves
Afterwards, solution becomes red from purple, as titration end-point.Record consumes dilute H2SO4Amount be H moles.Due to MgO with it is dilute
H2SO4The molar ratio of reaction is 1:1, according to dilute H2SO4Consumption understand MgO substance amount e.
Next, filter above-mentioned solution.Due to Ti and TiO2Dilute H is not dissolved under room temperature2SO4, therefore can be by Ti and TiO2It removes
It goes.Solution is divided into three parts later.
First part of solution disodium ethylene diamine tetraacetate (ethylenediaminetetraacetic acid) is titrated, measures Mg2+Substance amount X.First will
The pH value of solution is adjusted to 10 or so, adds in metal indicator (such as eriochrome black T) later, and utilize disodium ethylene diamine tetraacetate
Solution carries out being titrated to titration end-point, records the consumption of disodium ethylene diamine tetra-acetic acid solution.In pH=10, ethylenediamine tetrem
Magnesium ion generation stable comple in acid disodium and water, indicator eriochrome black T also can generate grape wine red with magnesium ion and be complexed
Object, the complex compound that stability is generated not as good as EDTA with magnesium ion.When being titrated with EDTA close to terminal, EDTA is from eriochrome black T
Capture magnesium ion with the complex compound of magnesium ion and chromium black T indicator is made to dissociate, therefore, solution becomes blue from claret, as
Terminal.
The complex reaction of eriochrome black T and magnesium is as follows：Mg2++Hlnd2-=Mglnd-+H+；
The complex reaction formula of EDTA and magnesium is as follows：Mglnd-+H2Y2-=MgY2-+H++Hlnd2-
Wherein Hlnd2-For chromium black T indicator (blue)；Mglnd-For the complex compound of magnesium ion and eriochrome black T (claret)；
H2Y2-For ethylenediamine tetra-acetic acid ion (colourless).
By above-mentioned reaction equation it is found that it is 1 that the complexing of EDTA and magnesium ion, which is compared,.Therefore equation 3X=c+d+e can be obtained, thus
D can be calculated.
Later, by second part of solution mercuric nitrate complexometry, following reaction occurs：
Hg++Cl-=HgCl (precipitation)
The quality of precipitation is measured to calculate Cl-Substance amount Y.It can thus be concluded that equation 3Y=2a+3b+2d, but the equation
There are two unknown quantitys, such as to calculate each component content, still need to another relational expression.
Next, third part solution is measured to the substance of whole Ti ions with inductive coupling plasma emission spectrograph
Amount Z.It can thus be concluded that equation 3Z=a+b.
TiCl can be calculated according to the last two steps2Substance amount a and TiCl3Substance amount b.
The content of each impurity can be calculated according to relation above：
TiCl4Quality for M1-M2, mass percentage is (M1-M2)/M1*100%
The amount of the substance of Mg is c, and mass percentage is：24c/M1*100%
The amount of the substance of MgO is e moles, and mass percentage is：40e/M1*100%
MgCl2Substance amount for d=3X-H moles, mass percentage is：95* (3X-H)/M1*100%
TiCl3Substance amount for b=3Y-6Z-6X+2H moles, mass percentage is：MTiCl3 (3Y-6Z-6X+
2H)/M1*100%
TiCl2Substance amount for a=9Z-3Y+6X-2H moles, mass percentage is：MTiCl2 (9Z-3Y+6X-
2H)/M1*100%
By the principle of the present invention it is found that other acid, which may be used, replaces dilute sulfuric acid, but cannot introduce Cl as the acid substituted
Element, and MgO therein can only be dissolved.In addition, the measure for Mg, Cl, Ti can also be realized with different modes.
Illustrate the method for detecting impurities of the present invention with reference to specific embodiment.
The preparation process of titanium sponge is：Weigh magnesium grain and TiCl4Each 20g is positioned over graphite crucible, and crucible is replaced with argon gas
Interior air, the lid for covering tightly graphite crucible are sealed reaction environment.Crucible is positioned in vacuum drying oven, covers bell,
The air in entire stove is replaced with argon gas again.Heating rate is controlled in 11K/min or so, is warming up to 750 DEG C of heat preservation 30min, i.e.,
Obtain sponge titanium products.In the process, it is contemplated that Mg not exclusively melts and TiCl4Volatile, irritant tart flavour, therefore
Ensure that Mg is excessive in experiment, using mass ratio 1:1 is tested.
1) product of experiment gained is taken, weigh record 38.27g；
2) sample is dried to the record 36.65g that weighs with filter paper；
3) sample of drying is placed in container, is heated to 65 DEG C and adds in ethyl alcohol and iodine dissolving, collected with drainage
The hydrogen arrived, the quality for calculating Mg are 0.98g；
4) with dilute H2SO4Titration, until MgO all dissolves, acid indicator discoloration is titration end-point；
5) solution of filtering gained, removes insoluble substance, solution is divided into three parts；
6) it is titrated with disodium ethylene diamine tetraacetate (EDTA) for first part, measures Mg2+Content, the quality of MgO is calculated
For 1.43g；
7) second part with mercuric nitrate complexometry, measures Cl-Substance amount；
8) third part measures the amount of the substance of whole Ti ions with inductive coupling plasma emission spectrograph；
9) according to measurement result, the content MgCl of each impurity is calculated2For 1.09g, TiCl3For 0.62g, TiCl2For
0.40g。
The content of each impurity can be calculated by above-mentioned data.
Embodiment described above only expresses embodiments of the present invention, and description is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
It encloses.
Claims (10)
1. the detection method of impurity content in a kind of titanium sponge, which is characterized in that the method includes the following steps：
1) titanium sponge is weighed, records its initial mass；
2) titanium sponge is dried to removing TiCl with filter paper4Until, the titanium sponge after drying is weighed, its quality is recorded, based on initial
Quality goes out TiCl with the Mass Calculation after drying4Quality；
3) absolute ethyl alcohol and catalyst are added in into the sample of drying, and is heated to predetermined temperature, measures the amount for generating gas, root
The mole of metal Mg is calculated according to the amount of gas；
4) acid indicator is added in into the solution of step 3), with acidometric titration to titration end-point, according to the mole of the acid of consumption
Calculate the mole of MgO；
5) filtration step 4) obtained by solution, remove insoluble substance, and solution is divided into three parts；
6) pH value of first part of solution is adjusted to predetermined value, adds in metal indicator later, and utilize ethylenediamine tetra-acetic acid
Two sodium solutions carry out being titrated to titration end-point, record the consumption of disodium ethylene diamine tetra-acetic acid solution and according to ethylenediamine tetrem
The mole of MgO that the mole and step 4) for the metal Mg that the consumption of acid disodium solution, step 3) calculate calculate is counted
Calculate MgCl2Mole；
7) mercuric nitrate is added in into second part of solution to be titrated, measure the quality of precipitation to calculate the mole of Cl ions；
8) mole of whole Ti ions in third part solution from step 5) is measured；
9) TiCl in sample is calculated2And TiCl3Mole and mass fraction.
2. according to the method described in claim 1, it is characterized in that, TiCl in step 9)2And TiCl3Mole be according to step
It is rapid 1) in the TiCl that obtains4Quality, the MgCl that obtains in step 6)2Mole, mole of Cl ions that obtains in step 7)
The mole of Ti ions that obtains calculates in amount and step 8).
3. according to the method described in claim 1, it is characterized in that, catalyst includes iodine or mercury chloride, heating temperature in step 3)
Degree is at 60 DEG C or more.
4. according to the method described in claim 1, it is characterized in that, the body of generation gas is measured in step 3) using drainage
Product.
5. according to the method described in claim 1, it is characterized in that, acid indicator is purple reindeer moss in step 4).
6. according to the method described in claim 1, it is characterized in that, the predetermined value of pH value is 10 in step 6).
7. according to the method described in claim 1, it is characterized in that, metal indicator is eriochrome black T in step 6).
8. according to the method described in claim 1, it is characterized in that, inductively coupled plasma atomic emission is utilized in step 8)
Instrument measures the amount of Ti ions.
9. according to the method described in claim 1, it is characterized in that, acid used in step 3) and step 4) is dilute sulfuric acid.
10. according to claim 1-9 any one of them methods, which is characterized in that the titanium sponge is by magnesiothermic reduction-true
Sky distillation integral method is prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109765215A (en) * | 2019-03-29 | 2019-05-17 | 重庆科技学院 | The Raman spectrum quantitative analysis method of organic matter in titanium tetrachloride |
| CN110231430A (en) * | 2019-05-20 | 2019-09-13 | 中国船舶重工集团公司第七二五研究所 | A kind of ion chromatographic method for chloride content determination in titanium sponge |
| CN112378901A (en) * | 2020-10-27 | 2021-02-19 | 西北矿冶研究院 | Chemical analysis method for determining chloride ions in metal copper by utilizing behavior of generated molecular crystals to restrain specific ions |
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2017
- 2017-12-14 CN CN201711337745.7A patent/CN108226373A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109765215A (en) * | 2019-03-29 | 2019-05-17 | 重庆科技学院 | The Raman spectrum quantitative analysis method of organic matter in titanium tetrachloride |
| CN110231430A (en) * | 2019-05-20 | 2019-09-13 | 中国船舶重工集团公司第七二五研究所 | A kind of ion chromatographic method for chloride content determination in titanium sponge |
| CN112378901A (en) * | 2020-10-27 | 2021-02-19 | 西北矿冶研究院 | Chemical analysis method for determining chloride ions in metal copper by utilizing behavior of generated molecular crystals to restrain specific ions |
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