CN101576540B

CN101576540B - Synchronous analysis method of SO4<2->, SO3<2->, S2O6<2-> and S2O8<2-> in pyrolusite leaching solution

Info

Publication number: CN101576540B
Application number: CN2009100595834A
Authority: CN
Inventors: 苏仕军; 丁桑岚
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2009-06-12
Filing date: 2009-06-12
Publication date: 2012-05-09
Anticipated expiration: 2029-06-12
Also published as: CN101576540A

Abstract

The invention discloses a synchronous analysis method of SO4<2->, SO3<2->, S2O6<2-> and S2O8<2-> in a pyrolusite leaching solution, which mainly comprises the steps of: separating and removing part of SO4<2-> from a sample pyrolusite leaching solution with a BaCl2 solution with the mass concentration of 5 percent to 10 percent through a titration precipitation method and then filtering; calculating the content of SO4<2-> in filtration residue; analyzing filtrate by an IC chromatographic instrument; adopting a AS14 anion analytical column which is subjected to gradient elution by leacheate prepared by ionized water and NaOH solution with the mass concentration of 15 to 50 mol/L; measuring the standard substance retention time and peak area of SO4<2->, SO3<2->, S2O6<2-> and S2O8<2-> by the IC chromatographic instrument; and comparing the retention time and peak area with the measured result of the filtrate so as to obtain the content of each sulphur-containing anion in the filtrate, and then adding with the amount of SO4<2-> obtained by calculation of the filtration residue to obtain the content of each sulphur-containing anion in the sample pyrolusite leaching solution. The adoption of the method for analyzing the content of sulphur-containing anion is characterized by fast speed, high accuracy, small error, good reproducibility and the like.

Description

SO in the pyrolusite leaching solution 42-, SO 32-, S 2O 62-, S 2O 82-Synchronized analyzing method

Technical field

The present invention relates to the content of sulphur-containing anion analysis measurement method, more specifically, relate to a kind of with SO in the chromatography of ions Synchronization Analysis pyrolusite leaching liquid ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Method.

Background technology

The liquid phase reactor of sulphuric dioxide and pyrolusite is complicated, and the form that exists of sulphur comprises SO in the leachate ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Etc. multiple, expression system reaction kinetics and acquisition engineering design parameter all need be with SO in the leachate ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Accurately concentration is foundation.But present analytical approach is many to be main with the chemical analysis method based on distillation-iodimetric titration, not only is difficult to Synchronization Analysis SO ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-, and error is bigger, and general error is greater than 3%.U.S. Lloyd M.Petrie, M.Emmelyn.Jakel etc. once reported and adopted SO in the ion chromatography analysis pyrolusite infusion solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-Three kinds of ions, but the method that this report adopts is for high concentration SO ₄ ^2-Do not take the pre-service measure, occur SO easily ₄ ^2-Detect the phenomenon that the too high influence in peak is measured, and this method do not adopt gradient elution, for Cl ^-Be difficult to reach quantitative requirement etc. main interfering material.

Summary of the invention

To the deficiency that the pyrolusite leachate sulfur-containing anion analytical approach of prior art exists, the object of the invention is intended to set up SO in a kind of fast and reliable, the simple and easy to do analysis pyrolusite leaching liquid ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-New method.

SO in the Synchronization Analysis pyrolusite leaching solution disclosed by the invention ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-The method of ion mainly comprises following measuring process:

(1) with the BaCl of mass concentration 5%～10% ₂Solution separates with the titration precipitation method removes part SO in the sample pyrolusite leaching solution ₄ ^2-, the SO in solution ₄ ^2-Be lower than 10g/L, filter then, calculate SO in the filter residue ₄ ^2-Content, gained filtrating is for use;

(2) filtrating is analyzed with the IC chromatograph; Adopt AS14 anion analysis post; Using deionized water and mass concentration is that the leacheate that 15～50mol/LNaOH solution is mixed with is no less than 2 drip washing to the AS14 anion analysis post that is injected with filtrating, and the leacheate flow control is 0.2～0.5ml/min, and the time of each drip washing is controlled at 5～30min; The mass content 65～85% of deionized water in the leacheate, the mass content 15～35% of NaOH solution;

(3) use the SO that measures by the IC chromatograph ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-The measurement result of standard substance retention time and peak area and filtrating relatively draws SO in the filtrating ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content;

(4) SO that step (3) is obtained ₄ ^2-Amount adds the SO that step (1) obtains ₄ ^2-Amount is promptly measured the amount that the sample pyrolusite leaches various anions containing sulfurs in the solution.

In order to obtain better analysis to measure effect, the present invention also can further take following technical measures:

The sample pyrolusite leaching solution that is used for analysis to measure can be earlier with filtering behind the speed oscillation 30～45min of oscillator with 150～200r/min again.

Sample pyrolusite leaching solution after vibration preferably filters mocromembrane with water system and filters.

The AS14 anion analysis post that is injected with filtrating preferably carries out repeatedly drip washing with having variable concentrations gradient elution liquid.The gradient elution preferred version preferably; Earlier with mass content 70% deionized water and leacheate drip washing 5～10min of constituting by mass content 30%NaOH solution; Constitute leacheate drip washing operation 5～10min with mass content 80% deionized water and mass content 20%NaOH solution then, constitute leacheate drip washing 15～30min with mass content 70% deionized water and mass content 30%NaOH solution more afterwards.

Lessivation, the temperature of analytical column and the temperature of detection cell preferably are controlled at 28～32 ℃ of scopes; The sample size that filtrating is injected AS14 anion analysis post preferably is controlled at 10～30 μ L; Measure Current Control at 15～35mA.

The chromatographic guard column of IC preferentially adopts AG14 model guard column; Detecting device preferentially adopts electric conductivity detector.

The present invention compares with the analysis measurement method of prior art, has the outstanding technique effect of ten minutes of following aspect:

(1) adopts BaCl ₂The quantitative precipitate and separate part of solution titration SO ₄ ^2-, can avoid high concentration SO ₄ ^2-To the damage of ion column, and SO ₄ ^2-Detect the phenomenon that the too high influence in peak is measured.

(2) in order to obtain better separating effect, the present invention has adopted gradient elution.Gradient elution can let main interfering material Cl ^-Reach quantitative requirement.

(3) adopt method of the present invention to the SO in the pyrolusite leaching liquid ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content carries out assay determination, and speed is fast, degree of accuracy is high, error is little, favorable reproducibility, and fast and reliable is simple and easy to do.

Embodiment

Below through embodiment the present invention is done further specific descriptions.Be necessary to be pointed out that at this; Following embodiment only is used for the present invention is done further explanation; Can not be interpreted as restriction to protection domain of the present invention; Affiliated art skilled is made some nonessential improvement and adjustment according to the foregoing invention content to the present invention, should still belong to protection scope of the present invention.

Embodiment 1

Pipette pyrolusite leaching solution 25mL to be measured and mass concentration 5%BaCl with pipettor respectively ₂Solution 10mL in receiving flask, stopper beyond the Great Wall, with oscillator with the speed oscillation 45min of 150r/min about after, filter mocromembrane with 0.45 μ m water system again and filter.Calculate SO in the filter residue ₄ ^2-Content.Gained filtrating is analyzed with the IC chromatograph.Chromatographic condition is: the stratographic analysis post is an AS14 anion analysis post, and guard column is AG14, and rejector is ASRS-ULTRA, and detecting device is an electric conductivity detector, and column temperature and detection cell temperature are about 28 ℃; Sample size is 25 μ L; Sample injection time is about 1.5min, and electric current is 17mA, and leacheate is the 25mol/LNaOH solution composition by deionized water and mass concentration; The leacheate flow is about 0.4ml/min; Adopt gradient elution liquid wash-out, the gradient elution process is: about the leacheate equilibrium elution 7min with mass content 70% deionized water and mass content 30%NaOH solution formation, use then about the leacheate drip washing 8min of mass content 80% deionization and mass content 20%NaOH solution composition earlier; Leacheate becomes the leacheate by mass content 70% deionized water and mass content 30%NaOH solution composition more afterwards, about drip washing operation 20min.Qualitative according to the standard substance retention time, adopt external standard method, draw SO in the filtrating according to peak area ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content quantitative is added the SO that is calculated by filter residue ₄ ^2-Amount, i.e. assay determination goes out the SO in the pyrolusite leaching liquid ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content.

Embodiment 2

Pipette pyrolusite leaching solution 25mL to be measured and mass concentration 8%BaCl with pipettor respectively ₂Solution 10mL in receiving flask, stopper beyond the Great Wall, with oscillator with the speed oscillation 30min of 200r/min about after filter mocromembrane with 0.45 μ m water system again and filter.Calculate SO in the filter residue ₄ ^2-Content, gained filtrating is analyzed with the IC chromatograph.Chromatographic condition is: the stratographic analysis post is an AS14 anion analysis post, and guard column is AG14, and rejector is ASRS-ULTRA, and detecting device is an electric conductivity detector, and column temperature and detection cell temperature are 31 ℃; Sample size is 20 μ L; Sample injection time is about 1.6min, and electric current is 25mA, and leacheate is the 35mol/LNaOH solution composition by deionized water and mass concentration; The leacheate flow is about 0.3ml/min; Adopt gradient elution liquid wash-out, the gradient elution process is: about the leacheate equilibrium elution 8min with mass content 70% deionized water and mass content 30%NaOH solution formation, use then about the leacheate drip washing 7min of mass content 80% deionization and mass content 20%NaOH solution composition earlier; Leacheate becomes the leacheate by mass content 70% deionized water and mass content 30%NaOH solution composition more afterwards, about drip washing operation 25min.Qualitative according to the standard substance retention time, adopt external standard method, draw SO in the filtrating according to peak area ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content quantitative is added the SO that is calculated by filter residue ₄ ^2-Content, i.e. assay determination goes out SO in the pyrolusite leaching liquid ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Content.

Claims

1. a pyrolusite leaches SO in the solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method, its characteristic mainly comprises following measuring process:

(2) filtrating is analyzed with the IC chromatograph; Filtrating is injected AS14 anion analysis post; Adopt gradient elution, lessivation is: the leacheate equilibrium elution 7～8min that constitutes with mass content 70% deionized water and mass content 30%NaOH solution earlier, the leacheate drip washing 7～8min that constitutes with mass content 80% deionized water and mass content 20%NaOH solution then; Constitute leacheate with mass content 70% deionized water and mass content 30%NaOH solution more afterwards; Drip washing operation 20～25min, the leacheate flow control is 0.2～0.5ml/min, the temperature of analytical column and the temperature of detection cell are 28～32 ℃.

(4) SO that step (3) is obtained ₄ ^2-Amount adds the SO that step (1) obtains ₄ ^2-Amount is promptly measured the amount that the sample pyrolusite leaches various anions containing sulfurs in the solution;

2. SO in the pyrolusite leaching solution according to claim 1 ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method is characterized in that sample pyrolusite leaching solution filters again behind the speed oscillation 30～45min of oscillator with 150～200r/min.

3. SO in the pyrolusite leaching solution according to claim 2 ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method is characterized in that the mocromembrane filtration is filtered by the sample pyrolusite leaching solution with water system after vibration.

4. according to SO in claim 1 or the 2 or 3 described pyrolusite leaching solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method, the sample size that injects AS14 anion analysis post that it is characterized in that filtrating is 10～30 μ L.

5. according to SO in claim 1 or the 2 or 3 described pyrolusite leaching solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method, it is characterized in that measuring electric current is 15～35mA.

6. according to SO in claim 1 or the 2 or 3 described pyrolusite leaching solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method is characterized in that the chromatographic guard column of IC is an AG14 model guard column.

7. according to SO in claim 1 or the 2 or 3 described pyrolusite leaching solution ₄ ^2-, SO ₃ ^2-, S ₂O ₆ ^2-, S ₂O ₈ ^2-Synchronized analyzing method is characterized in that the chromatographic detecting device of IC is an electric conductivity detector.