阅读说明：本技术 一种快速测定钛铁中钛含量的方法 (Method for rapidly measuring titanium content in ferrotitanium ) 是由 周景涛 战丽君 梁艳芳 成永杰 于 2020-12-10 设计创作，主要内容包括：本发明公开了一种快速测定钛铁中钛含量的方法,其包括：向盛有试样的锥形瓶中加入稀硫酸、盐酸,低温分解试样,随后在隔绝空气的条件下用金属铝还原,加入滴定指示剂,用硫酸铁铵标准溶液滴定至稳定的红色,根据硫酸铁铵标准滴定溶液的消耗量计算试样中钛的含量。本发明提供的方法分析设备简单,操作易掌握,分析效率高,同时能保证检测结果的准确性,可以满足现场快节奏生产的需求。(The invention discloses a method for rapidly measuring the titanium content in ferrotitanium, which comprises the following steps: adding dilute sulfuric acid and hydrochloric acid into a conical flask containing the sample, decomposing the sample at low temperature, reducing the sample by using metal aluminum under the condition of isolating air, adding a titration indicator, titrating the sample to a stable red color by using an ammonium ferric sulfate standard titration solution, and calculating the content of titanium in the sample according to the consumption of the ammonium ferric sulfate standard titration solution. The method provided by the invention has the advantages of simple analysis equipment, easiness in operation mastering and high analysis efficiency, can ensure the accuracy of the detection result, and can meet the requirement of on-site fast-paced production.)

1. A method for rapidly measuring the titanium content in ferrotitanium is characterized by comprising the following steps: adding dilute sulfuric acid and hydrochloric acid into a conical flask containing the sample, decomposing the sample at low temperature, reducing the sample by using metal aluminum under the condition of isolating air, adding a titration indicator, titrating the sample to a stable red color by using an ammonium ferric sulfate standard titration solution, and calculating the content of titanium in the sample according to the consumption of the ammonium ferric sulfate standard titration solution.

2. The method according to claim 1, characterized in that the volumetric mass ratio between the addition of the dilute sulphuric acid and hydrochloric acid and the quantity of the sample is: 130-150 ml, 50-70 ml, 0.5000 g.

3. The method according to claim 1 or 2, wherein the dilute sulfuric acid is a sulfuric acid solution obtained by mixing concentrated sulfuric acid and water at a volume ratio of 1:5, and the hydrochloric acid is a hydrochloric acid solution obtained by mixing hydrochloric acid and water at a volume ratio of 1: 1.

4. A method according to any of claims 1-3, characterized in that the air-insulated operating method is: sodium bicarbonate was added to the sample solution obtained by decomposing the sample at low temperature, and the mouth of the flask was covered with a porcelain crucible.

5. The method according to claim 4, wherein the ratio of the amount of the sodium bicarbonate to the amount of the sample is (1-2): 1.

6. The method of any one of claims 1-5, wherein the titration indicator is an ammonium thiocyanate indicator.

7. The method according to any one of claims 1 to 6, wherein the formula for calculating the titanium content in the sample from the consumption of the standard titration solution of ferric ammonium sulfate is:

in the formula: t: the concentration of the ammonium ferric sulfate standard titration solution is mg/mL;

v: the sample consumes the volume of the standard titration solution of ammonium ferric sulfate, mL;

V₀: the blank consumed volume of ammonium ferric sulfate standard titration solution, mL.

m: sample mass, g.

8. The method according to any one of claims 1 to 7, wherein the standard titration solution of ferric ammonium sulfate is prepared by: 50g of ferric ammonium sulfate (FeNH) are weighed₄(SO₄)₂·12H₂O) is placed in a 500mL beaker, 200mL of water is added, 50mL of (1+1) sulfuric acid is dissolved, and then the solution is added to a 1000mL volumetric flask and mixed and shaken uniformly.

9. The method according to claim 8, wherein the concentration of the standard titration solution of ferric ammonium sulfate is calculated by the formula:

in the formula, T: the concentration of the ammonium ferric sulfate standard titration solution is mg/mL;

W_{ti label}Percent: titanium content,%, of the ferrotitanium standard sample;

m₁: weighing the ferrotitanium standard sample, and g;

V₁: the ferrotitanium standard sample consumes the volume of ammonium ferric sulfate standard titration solution, mL;

V₀₁: the blank solution consumed the volume of the standard titration solution of ferric ammonium sulfate, mL.

10. Method according to any one of claims 1 to 9, characterized in that it comprises in particular the steps of:

(1) decomposition sample

Weighing 0.5000g of sample, placing the sample in a 500mL conical flask, adding 140mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 60mL of (1+1) hydrochloric acid, adding 1g of aluminum sheet after the sample is dissolved, adding about 0.5g of sodium bicarbonate, immediately covering a ceramic crucible cover on the opening of the conical flask, heating and dissolving the sample on a low-temperature electric furnace, boiling for 5-6 min after the sample is dissolved, taking down and cooling;

(2) measurement of

Taking down the ceramic crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the mauve disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the mauve disappears, and fully oscillating to keep the mauve not to disappear for 2 min.

Technical Field

The invention belongs to the technical field of alloy analysis, and particularly relates to a method for rapidly measuring titanium content in ferrotitanium.

Background

Ferrotitanium is generally used as a deoxidizer and a degasifier in the steel-making process. The deoxidation capacity of titanium is higher than that of silicon and manganese, the composition segregation of steel ingots can be reduced, the quality of the steel ingots is improved, and meanwhile, ferrotitanium can be used as an alloy agent in the steelmaking process to enhance the strength, corrosion resistance and stability of steel; the casting technology can improve the wear resistance, stability and processability of cast iron. The titanium content in the ferrotitanium needs to be accurately and rapidly provided in the production process of the process.

The method for measuring the content of titanium in ferrotitanium at present is mainly an ammonium ferric sulfate titration method adopted in the national standard GB/T4701.1-2009, a volumetric method is adopted in the method, sample decomposition is carried out by dissolving sulfuric acid and hydrochloric acid and hydrofluoric acid, acidifying with nitric acid, smoking with sulfuric acid and acidifying with hydrochloric acid, a sodium hydroxide precipitation solution is required to treat interference elements, the method is complicated, the efficiency is low, the operation is not easy to master, the standard titration solution of the ammonium ferric sulfate is calibrated by using a titanium standard solution, and the condition that a ferrotitanium matrix interferes with a measurement result needs to be considered, so that the national standard method is not suitable for the requirement of rapid analysis of a technological process.

Disclosure of Invention

In view of one or more of the problems in the prior art, the present invention provides a method for rapidly determining the titanium content in ferrotitanium, which comprises: adding dilute sulfuric acid and hydrochloric acid into a conical flask containing the sample, decomposing the sample at low temperature, reducing the sample by using metal aluminum under the condition of isolating air, adding a titration indicator, titrating the sample to a stable red color by using an ammonium ferric sulfate standard titration solution, and calculating the content of titanium in the sample according to the consumption of the ammonium ferric sulfate standard titration solution.

The volume mass ratio of the addition amount of the dilute sulfuric acid and the hydrochloric acid to the amount of the sample is as follows: 130-150 ml, 50-70 ml, 0.5000 g.

The dilute sulfuric acid is a sulfuric acid solution obtained by mixing concentrated sulfuric acid and water according to the volume ratio of 1:5, and the hydrochloric acid is a hydrochloric acid solution obtained by mixing hydrochloric acid and water according to the volume ratio of 1: 1.

The operation method of the air isolation comprises the following steps: sodium bicarbonate was added to the sample solution obtained by decomposing the sample at low temperature, and the mouth of the flask was covered with a porcelain crucible.

The ratio of the amount of sodium bicarbonate added to the amount of the sample is (1-2): 1.

The titration indicator is an ammonium thiocyanate indicator.

In the method, the calculation formula for calculating the titanium content in the sample according to the consumption of the standard titration solution of ferric ammonium sulfate is as follows:

in the formula: t: the concentration of the ammonium ferric sulfate standard titration solution is mg/mL;

v: the sample consumes the volume of the standard titration solution of ammonium ferric sulfate, mL;

V₀: the blank consumed volume of ammonium ferric sulfate standard titration solution, mL.

m: sample mass, g.

The preparation method of the standard titration solution of ferric ammonium sulfate comprises the following steps: 50g of ferric ammonium sulfate (FeNH) are weighed₄(SO₄)₂·12H₂O) is placed in a 500mL beaker, 200mL of water is added, 50mL of (1+1) sulfuric acid is dissolved, and then the solution is added to a 1000mL volumetric flask and mixed and shaken uniformly.

The calculation formula of the concentration of the standard titration solution of ferric ammonium sulfate is as follows:

in the formula, T: the concentration of the ammonium ferric sulfate standard titration solution is mg/mL;

W_{ti label}Percent: titanium content,%, of the ferrotitanium standard sample;

m₁: weighing the ferrotitanium standard sample, and g;

V₁: the ferrotitanium standard sample consumes the volume of ammonium ferric sulfate standard titration solution, mL;

V₀₁: the blank solution consumed the volume of the standard titration solution of ferric ammonium sulfate, mL.

The method specifically comprises the following steps:

(1) decomposition sample

Weighing 0.5000g of sample, placing the sample in a 500mL conical flask, adding 140mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 60mL of (1+1) hydrochloric acid, adding 1g of aluminum sheet after the sample is dissolved, adding about 0.5g of sodium bicarbonate, immediately covering a ceramic crucible cover on the opening of the conical flask, heating and dissolving the sample on a low-temperature electric furnace, boiling for 5-6 min after the sample is dissolved, taking down and cooling;

(2) measurement of

Taking down the ceramic crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the mauve disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the mauve disappears, and fully oscillating to keep the mauve not to disappear for 2 min. The ammonium thiocyanate indicator is a complexing indicator, and titanium ions are not consumed, so that titration deviation cannot be caused, and the determination result is more accurate.

Compared with the prior art, the method has the following effects:

(1) the invention has the advantages of less sample usage amount and less reagent variety usage, can achieve the purpose of completely decomposing the sample only by using dilute sulphuric acid and hydrochloric acid at low temperature, and overcomes the pollution problem caused by decomposing the sample by a large amount of reagents and various reagents.

(2) The method adopts the porcelain crucible cover to replace the Geiger funnel with a complex structure, thereby solving the dilemma of purchasing the Geiger funnel at high cost.

(3) The method adopts 2-3 ferrotitanium standard samples of the same variety to calibrate the ferric ammonium sulfate standard titration solution, and eliminates the influence of different matrixes on the result accuracy.

(4) The method has short analysis time, is easy to be mastered by operators, and the analysis result meets the field production requirement. The method provides a detection method for rapidly analyzing the titanium content in the ferrotitanium, has short analysis time limit and accurate analysis result, and is suitable for modern industrial production analysis.

Detailed Description

The present invention will be described in detail with reference to specific examples.

In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the following description is to be regarded as illustrative in nature and not as restrictive.

The various biological materials described in the examples are obtained by way of experimental acquisition for the purposes of this disclosure only and should not be limiting as to the source of the biological material of the present invention. In fact, the sources of the biological materials used are wide and any biological material that can be obtained without violating the law and ethics can be used instead as suggested in the examples.

The preparation method and concentration calibration method of the standard titration solution of ferric ammonium sulfate used in the following examples are as follows: 50g of ferric ammonium sulfate (FeNH) are weighed₄(SO₄)₂·12H₂O) is placed in a 500mL beaker, 200mL of water is added, 50mL of (1+1) sulfuric acid is dissolved, and then the solution is added to a 1000mL volumetric flask and mixed and shaken uniformly.

Calibrating an ammonium ferric sulfate standard titration solution: adopting 2-3 ferrotitanium standard samples of the same variety (such as a ferrotitanium standard sample standard value 37.17% numbered ECRM584-1, a ferrotitanium standard value 43.81% numbered YSBC19604-05, a ferrotitanium standard sample standard value 27.15% numbered VSF42, and a ferrotitanium standard sample standard value 31.90% numbered VSF 43), decomposing the samples and measuring the titanium content in the samples according to the following operation steps to calibrate the concentration of the ammonium ferric sulfate standard titration solution:

(1) decomposition sample

Weighing 0.5000g of ferrotitanium standard sample according to the titanium content, placing the ferrotitanium standard sample in a 500mL conical flask, adding 140mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 60mL of (1+1) hydrochloric acid, adding 1g of aluminum sheet after the sample is dissolved, adding about 0.5g of sodium bicarbonate, immediately covering a ceramic crucible cover, and heating and dissolving on a low-temperature electric furnace. After dissolving, boiling for 5-6 min, taking down and cooling.

(2) Measurement of

Taking down the ceramic crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the mauve disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the mauve disappears, and fully oscillating to keep the mauve not to disappear for 2 min.

The concentration of the standard titration solution of ferric ammonium sulfate was calculated by the following formula:

in the formula, T: the concentration of the ammonium ferric sulfate standard titration solution is mg/mL;

W_{ti label}Percent: titanium content,%, of the ferrotitanium standard sample;

m₁: weighing the ferrotitanium standard sample, and g;

V₁: the ferrotitanium standard sample consumes the volume of ammonium ferric sulfate standard titration solution, mL;

V₀₁: the blank solution consumed the volume of the standard titration solution of ferric ammonium sulfate, mL.

Example 1: method for rapidly measuring titanium content in ferrotitanium

Weighing 0.5000g of ferrotitanium standard sample (YSBC18604-08), placing the sample in a 500mL conical flask, adding 140mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 60mL of (1+1) hydrochloric acid, adding 1g of aluminum sheet after the sample is dissolved, adding about 0.5g of sodium bicarbonate, immediately covering a ceramic crucible cover on the mouth of the conical flask, and heating and dissolving the mixture on a low-temperature electric furnace. After dissolving, boiling for 5-6 min, taking down and cooling, taking down the porcelain crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the purple red disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the purple red disappears, and fully oscillating to keep the red color for 2min as the end point. The measurement result was 28.2%, the standard value was 27.93%, and the analysis time was about 3.0 to 3.5 hours.

The ferrotitanium standard substance is weighed and is measured according to GB/T4701.1-2009, the measurement result of the sample is 28.15%, the standard value is 27.93%, and the analysis time is about 7-7.5 hours.

Example 2: method for rapidly measuring titanium content in ferrotitanium

0.5000g of a ferrotitanium standard sample (YSBC19605-04) is weighed into a 500mL conical flask, 140mL of (1+5) sulfuric acid is added, the sample is dissolved at low temperature, 60mL of (1+1) hydrochloric acid is added, 1g of aluminum sheet is added after the sample is dissolved, about 0.5g of sodium bicarbonate is added, a ceramic crucible cover is immediately covered, and the mixture is heated and dissolved on a low-temperature electric furnace. After dissolving, boiling for 5-6 min, taking down and cooling, taking down the porcelain crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the purple red disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the purple red disappears, and fully oscillating to keep the red color for 2min as the end point. The measurement result was 38.60%, the standard value was 38.81%, and the analysis time was about 3.0 to 3.5 hours.

The ferrotitanium standard substance is weighed and measured according to GB/T4701.1-2009, the measurement result of the sample is 38.50%, the standard value is 38.81%, and the analysis time is about 7-7.5 hours.

Example 3: method for rapidly measuring titanium content in ferrotitanium

Weighing 0.5000g of ferrotitanium sample, placing the ferrotitanium sample in a 500mL conical flask, adding 140mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 60mL of (1+1) hydrochloric acid, adding 1g of aluminum sheet after the sample is dissolved, adding about 0.5g of sodium bicarbonate, immediately covering a ceramic crucible cover, and heating and dissolving on a low-temperature electric furnace. After dissolving, boiling for 5-6 min, taking down and cooling, taking down the porcelain crucible cover, immediately adding 20mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the purple red disappears, adding 5mL of 50g/L ammonium thiocyanate solution, continuously titrating until the purple red disappears, and fully oscillating to keep the red color for 2min as the end point. The results of the measurements of the two replicates were 22.50% and 22.46%, respectively, and the analysis time was about 3.0-3.5 hours.

Example 4: method for rapidly measuring titanium content in ferrotitanium

Weighing 0.1000g of a ferrotitanium sample, placing the ferrotitanium sample in a 100mL conical flask, adding 35mL of (1+5) sulfuric acid, dissolving the sample at low temperature, adding 12mL of (1+1) hydrochloric acid, adding 0.2g of aluminum sheet after the sample is dissolved, adding about 0.1g of sodium bicarbonate, immediately covering a ceramic crucible cover, and heating and dissolving on a low-temperature electric furnace. After dissolving, boiling for 5-6 min, taking down and cooling, taking down the porcelain crucible cover, immediately adding 5mL of saturated ammonium sulfate solution, immediately titrating with a standard titration solution of ferric ammonium sulfate until the purple red disappears, adding 1mL of 50g/L ammonium thiocyanate solution, continuously titrating until the purple red disappears, and fully oscillating to keep the red color for 2min as the end point. The results of the measurements on the two replicates were 23.44% and 23.52%, respectively, and the analysis time was about 50 minutes.

From the results, the method for rapidly determining the content of the titanium and the titanium has high accuracy and good repeatability. Compared with the prior art, the method has high analysis speed and is more suitable for the field process analysis requirement.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.