CN106198767B - The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid - Google Patents
The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid Download PDFInfo
- Publication number
- CN106198767B CN106198767B CN201510216443.9A CN201510216443A CN106198767B CN 106198767 B CN106198767 B CN 106198767B CN 201510216443 A CN201510216443 A CN 201510216443A CN 106198767 B CN106198767 B CN 106198767B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- liquid
- electroplate liquid
- detection
- acid content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The present invention relates to the detection methods of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid.The technical problem that mainly the mass content detection accuracy of sulfuric acid is low in tin methane sulfonate system electroplate liquid in solution traditional technology, detection time is long, detection is cumbersome, detection the degree of automation is low.The technical solution of the present invention is as follows: in a kind of tin methane sulfonate system electroplate liquid sulfuric acid content detection method, comprising the following steps: (1) determine sulfuric acid content liquid chromatographic detection condition in electroplate liquid；(2) sulfuric acid standard curve is drawn；(3) prepare liquid is prepared；(4) to sulfuric acid liquid-phase chromatographic analysis in plating liquor；(5) sulfuric acid content in electroplate liquid to be measured is calculated.The method of the present invention is without complicated sample pre-treatments, and easy to operate, precision is good, and accuracy is high, and high degree of automation can quickly measure sulfuric acid mass content in tin methane sulfonate system electroplate liquid, meet the detection requirement of cold rolling tin-plated product production technology.
Description
Technical field
The invention belongs to chemical analysis technology fields, and in particular to the detection method of cold rolling electroplating tin electroplate liquid, especially
It is related to the detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid.
Background technique
As cold rolling electroplating tin steel plate plate electroplating technology is constantly progressive, the raising that environmental protection index requires, traditional phenol sulphur
Contain phenyl ring in sour (PSA) electroplate liquid, not only there is toxicity, postorder liquid waste processing difficulty is big, and process of tin has been electroplated not in PSA
It is able to satisfy environmental requirement.Methanesulfonate tin deposit technique is a kind of novel process developed in recent years, its electroplate liquid is nontoxic
Property there is environment-friendly function, and be suitable for the higher unit of speed, help to improve the yield of unit.
In order to guarantee that cold rolling electroplating tin steel plate steadily efficiently produces, it is necessary to constituents each in electroplate liquid are monitored,
Sulfuric acid mass content is one of its important indicator in middle electroplate liquid.Sulfuric acid can control the generation of tin mud in electroplate liquid, simultaneously also
The particle size of tin mud can be increased, sulfuric acid content control is 2 ~ 4g/l in electroplate liquid, and excessively high sulfuric acid content will lead to excessively high
Tin mud amount, too low sulfuric acid content also results in the increase of tin mud amount, while also affecting the filtration treatment of tin mud, therefore needs
Detect sulfuric acid content variation in monitoring electroplate liquid.
There is presently no corresponding national standard methods for sulfuric acid content detection method in methane sulfonic acid (MSA) tin system electroplate liquid
Or Industry methods, although some traditional sulfuric acid content determination methods are such as: acid base titration, gravimetric method, photometry these
Detection method, but since tin methane sulfonate system electroplate liquid contains a large amount of methane sulfonic acids and surfactant, traditional analysis method
It is difficult to meet testing requirements, not only cumbersome, detection data precision is poor, and accuracy is not high, or even it is also possible to provide error
Data accidentally provide error message to sulfuric acid monitoring in electroplate liquid in production process, economic damage may be caused to smelter
It loses.
Chinese patent CN 200910311895.X, entitled, method for testing nitroso-sulfuric acid disclose a kind of nitroso
Sulfuric acid determination method, mainly according to potassium permanganate and nitrosylsulfuric acid redox reaction, by consuming potassium permanganate
Amount is to calculate nitrosylsulfuric acid content.It is complicated for operation that this method mainly shows the problem of the following aspects (1) this method, also
It is related to a large amount of chemical reagent, the operating time is considerably long；(2) this method is suitble to solution system to be measured relatively easy, interfering substance
It is few.And tin methane sulfonate system electroplate liquid system is relative complex more, containing a large amount of organic acid and organic matter etc., this method cannot expire
Sufficient electroplate liquid system testing requirements.(3) this method measurement is also in traditional measurement method, can operate difference, and the degree of automation is low,
It is difficult to meet the production requirement of modern steel enterprise.
In the prior art, disclosed sulfuric acid content detection method operates phase also in traditional manual inspection technological layer
When complicated, large labor intensity, poor operability, influence factor is more, and measurement accuracy and accuracy are lower, and detection time is long, difficult
To meet the fast pace production requirement of modern steel enterprise.
Summary of the invention
The object of the present invention is to provide the detection methods of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid, solve existing
The mass content detection accuracy of sulfuric acid is low in tin methane sulfonate system electroplate liquid in technology, detection time is long, detection is cumbersome, detects certainly
The low technical problem of dynamicization degree.
The technical solution adopted by the present invention is that:
The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid, comprising the following steps:
(1) sulfuric acid content liquid chromatographic detection condition in electroplate liquid is configured, sample collection liquid is 2 ~ 4ul, with ethylene bridge
Hybrid particulates are filler polyamide chromatographic column, and chromatogram column length 150mm, it is stream with acetonitrile-water phase that column temperature, which is 35 ~ 45 DEG C,
Dynamic phase, wherein the water phase is to contain 0.60g~0.85g ammonium acetate in 1000ml water phase, in 1000ml acetonitrile containing 0.60g~
0.85g ammonium acetate, gradient elution, acetonitrile-water phase volume ratio are 80:20~60:40, and flow velocity is 0.3ml/min~0.6ml/
min；Using evaporative light scattering detector, wherein flow rate of carrier gas pressure is 35 ~ 45MPa, and drift tube temperature is 60 ~ 70 DEG C；
(2) draw sulfuric acid standard curve with liquid chromatograph, pipette 1.000 respectively, 2.000,3.000,4.000,
5.000,6.000g sulfuric acid solution is diluted with water to scale in 1000ml volumetric flask, shakes up solution, is transferred in sample bottle,
According to detection and analysis of the liquid chromatograph condition to each standard solution in step (1), sulfuric acid standard solution liquid chromatogram is obtained
Spectrum and peak area draw unary linear regression equation lgm=a × lgA+b, determine a and b specific value, and wherein m is sulfuric acid quality
Content, unit g/l；A is that liquid chromatogram measures standard sulfuric acid standard solution peak area, and unit is mv min；A and b is immeasurable
Guiding principle coefficient；
(3) prepare prepare liquid, take electroplate liquid high purity water to be measured according to 1:1 dilution proportion after, be transferred in sample bottle, make
For at prepare liquid；
(4) to the carry out liquid-phase chromatographic analysis of prepare liquid, according to liquid phase chromatogram condition in step (1) to sulfuric acid in prepare liquid
Liquid-phase chromatographic analysis is carried out, sulfuric acid liquid chromatogram map and sulfuric acid peak area A are obtained；
(5) sulfuric acid content in electroplate liquid to be measured is calculated, sulfuric acid content is calculated according to formula one in electroplate liquid,Formula one, wherein m is sulfuric acid mass content in electroplate liquid to be measured, unit g/l；A is liquid chromatogram
Sulfuric acid peak area in electroplate liquid is measured, unit is that mv min, a and b are dimensionless factor, by the sulfuric acid standard curve drawn out
Unary linear regression equation determines.
The present invention uses ethylene bridge hybrid particulates for filler polyamide chromatographic column, using acetonitrile-water phase as mobile phase,
Sulfuric acid peak area is detected with evaporative light scattering detector after separating to sulfuric acid in electroplate liquid, calculates sulphur in electroplate liquid to be measured
Acid content, the mass content detection efficiency for solving sulfuric acid in existing tin methane sulfonate system electroplate liquid is low, poor accuracy, automation journey
Spend the problems such as low.
The present invention has following good effect compared with prior art:
1. the present invention realizes the mass content rapid and accurate determination of sulfuric acid in tin methane sulfonate system electroplate liquid, without multiple
Miscellaneous sample pre-treatments, it is easy to operate, labor intensity is low, strong operability, high degree of automation is detected, complicated behaviour is avoided
Make step, effectively separates sulfuric acid in sample with organic components other in electroplate liquid.
2. method of the invention has the characteristics that speed survey, efficient, high-throughput, environmental protection by using liquid chromatograph.
Specific embodiment
The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid, comprising the following steps:
(1) sulfuric acid content liquid chromatographic detection condition in electroplate liquid is configured, sample collection liquid is 2ul, accurately weighs 0.75g
Ammonium acetate (chromatographically pure) 1000ml high purity water dissolves, and stirs evenly and is configured to 0.075% ammonium acetate solution；Accurately weigh 0.75g second
Sour ammonium (chromatographically pure) is dissolved with 1000ml acetonitrile (chromatographically pure), is stirred evenly and is configured to 0.075% ammonium acetate acetonitrile solution；Using model
For the liquid chromatograph equipped with evaporative light scattering detector that ACQUITY UPLC, waters company, the U.S. are produced, chromatographic column is
Ethylene bridge hybrid particulates are filler polyamide chromatographic column, and length 150mm, column temperature is 40 DEG C, and the water phase of leacheate is
0.75% ammonium acetate solution, the organic phase of leacheate are 0.75% ammonium acetate acetonitrile solution, carry out gradient elution by table 1；Evaporation
The carrier gas of light scattering detector is argon gas, and argon gas velocity pressure is 40MPa, and drift tube temperature is 60 DEG C；
1 gradient elution parameter of table
(2) draw sulfuric acid standard curve with liquid chromatograph, pipette 1.000 respectively, 2.000,3.000,4.000,
5.000,6.000g sulfuric acid solution is diluted with water to scale in 1000ml volumetric flask, shakes up solution, is transferred in sample bottle,
According to detection and analysis of the liquid chromatograph condition to each standard solution in step (1), sulfuric acid standard solution liquid chromatogram is obtained
Spectrum and peak area draw unary linear regression equation lgm=a × lgA+b, determine a and b specific value, and wherein m is sulfuric acid quality
Content, unit g/l；A is that liquid chromatogram measures standard sulfuric acid standard solution peak area, and unit is mv min；A and b is immeasurable
Guiding principle coefficient；
(3) prepare prepare liquid, take 50ml electroplate liquid high purity water to be measured according to 1:1 dilution proportion after, be transferred to sample bottle
In, it is prepared into prepare liquid；
(4) to the carry out liquid-phase chromatographic analysis of prepare liquid, according to liquid phase chromatogram condition in step (1) to sulfuric acid in prepare liquid
Liquid-phase chromatographic analysis is carried out, sulfuric acid liquid chromatogram map and sulfuric acid peak area A are obtained；
(5) sulfuric acid content in electroplate liquid to be measured is calculated, sulfuric acid content is calculated according to formula one in electroplate liquid,Formula one, wherein m is sulfuric acid mass content in electroplate liquid to be measured, unit g/l；A is liquid chromatogram
Sulfuric acid peak area in electroplate liquid is measured, unit is that mv min, a and b are dimensionless factor, by the sulfuric acid standard curve drawn out
Unary linear regression equation determines.
The preci-sion and accuracy of the method for the present invention is confirmed by the recovery testu and Precision Experiment of sample.
Recovery experiment after a certain amount of sulfuric acid is added in Tin plating electrolyte sample, by the method for the present invention, detects adding for sample
The rate of recovery is marked, test result is shown in Table 2.
2 sample recovery testu of table
Precision Experiment carries out 11 Precision Experiments, analysis knot to sulfuric acid content in 2 groups of methanesulfonate tin deposit electroplate liquids
Fruit is shown in Table 3.
3 sample Precision Experiment g/l of table
It is above-mentioned the experimental results showed that, in the method for the present invention methanesulfonate tin deposit electroplate liquid the sulfuric acid content rate of recovery 98.7 ~
Between 101.8%, the rate of recovery is higher, and detection data counts RSD and is much smaller than 5%, and detection data precision is good, and method is accurate and reliable,
Fully meet iron and steel enterprise's production requirement.
Claims (1)
1. the detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid, characterized in that the method includes following steps
It is rapid:
(1) the liquid chromatographic detection condition of sulfuric acid content in electroplate liquid is configured, sample collection liquid is 2~4ul, miscellaneous with ethylene bridge
Change the polyamide chromatographic column that particle is filler, chromatogram column length 150mm, column temperature is 35~45 DEG C, is with acetonitrile-water phase
Mobile phase contains 0.60g in 1000ml acetonitrile wherein the water phase is to contain 0.60g~0.85g ammonium acetate in 1000ml water phase
~0.85g ammonium acetate, gradient elution, gradient elution parameter are shown in Table 1；Using evaporative light scattering detector, wherein flow rate of carrier gas pressure
Power is 35~45MPa, and drift tube temperature is 60~70 DEG C；
1 gradient elution parameter of table
(2) draw sulfuric acid standard curve with liquid chromatograph, pipette 1.000 respectively, 2.000,3.000,4.000,5.000,
6.000g sulfuric acid solution is diluted with water to scale in 1000ml volumetric flask, shakes up solution, is transferred in sample bottle, according to step
Suddenly liquid chromatograph condition tests and analyzes each standard solution in (1), obtains sulfuric acid standard solution liquid chromatogram map and peak face
Product draws unary linear regression equation lgm=a × lgA+b, determines a and b specific value, and wherein m is sulfuric acid mass content, single
Position is g/l；A is that liquid chromatogram measures standard sulfuric acid standard solution peak area, unit mvmin；A and b is dimensionless factor；
(3) prepare prepare liquid, take electroplate liquid high purity water to be measured according to 1:1 dilution proportion after, be transferred in sample bottle, be prepared into
Prepare liquid；
(4) liquid-phase chromatographic analysis is carried out to prepare liquid, liquid is carried out to sulfuric acid in prepare liquid according to liquid phase chromatogram condition in step (1)
Analysis of hplc obtains sulfuric acid liquid chromatogram map and sulfuric acid peak area A；
(5) sulfuric acid content in electroplate liquid to be measured is calculated, sulfuric acid content is calculated according to formula one in electroplate liquid,
Formula one, wherein m is sulfuric acid mass content in electroplate liquid to be measured, unit g/l；A is that liquid chromatogram measures sulfuric acid in electroplate liquid
Peak area, unit mvmin, a and b are dimensionless factor, by one-variable linear regression side in the sulfuric acid standard curve drawn out
Journey determines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510216443.9A CN106198767B (en) | 2015-04-30 | 2015-04-30 | The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510216443.9A CN106198767B (en) | 2015-04-30 | 2015-04-30 | The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106198767A CN106198767A (en) | 2016-12-07 |
| CN106198767B true CN106198767B (en) | 2019-07-19 |
Family
ID=57458193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510216443.9A Active CN106198767B (en) | 2015-04-30 | 2015-04-30 | The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106198767B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4673467A (en) * | 1986-09-02 | 1987-06-16 | Cbs Inc. | Method of manufacturing fine-grained copper substrate for optical information carrier |
| CN101363817A (en) * | 2008-05-23 | 2009-02-11 | 浙江大学宁波理工学院 | Method for detecting multi-brightener in liquid for brilliantly nickel plating |
-
2015
- 2015-04-30 CN CN201510216443.9A patent/CN106198767B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4673467A (en) * | 1986-09-02 | 1987-06-16 | Cbs Inc. | Method of manufacturing fine-grained copper substrate for optical information carrier |
| CN101363817A (en) * | 2008-05-23 | 2009-02-11 | 浙江大学宁波理工学院 | Method for detecting multi-brightener in liquid for brilliantly nickel plating |
Non-Patent Citations (4)
| Title |
|---|
| HPLC-ELSD法测定复方氨基葡萄糖片中硫酸软骨素的含量;林燕飞 等;《中国现代应用药学杂志》;20061031;第23卷(第5期);全文 |
| HPLC检测电镀液中有机残留物;张昌鸣 等;《电镀与环保》;19870731;第7卷(第4期);全文 |
| Optimization of the Sulfuric Acid-Catalyzed Estolide Synthesis from Oleic Acid;Terry A.Isbell et al.;《JAOCS》;19971231;第74卷(第4期);全文 |
| 高效液相色谱-蒸发光散射检测法测定氨基糖普类抗生素中硫酸盐含量的研究;刘浩 等;《药物分析杂志》;20011231;第21卷(第6期);全文 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106198767A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102914600B (en) | Method for measuring trace chloridion and sulfate radical in loprazolam samples by ion chromatography | |
| CN103969392A (en) | High performance liquid chromatographic analysis method for pyromellitic dianhydride | |
| CN108802256B (en) | Method for detecting content of monoethanolamine | |
| CN109444282B (en) | Method for determining content of active substances in petroleum sulfonate sample of Daqing oil field by liquid chromatography | |
| CN105606738A (en) | HPLC (High Performance Liquid Chromatography) analysis method for sodium 3,3'-dithiodipropane sulfonate | |
| CN111537657A (en) | Method for detecting content of trace metal ions in high-purity thiourea by ion chromatography | |
| CN112684030A (en) | Method for detecting perfluoroalkanoic acid compound in aquatic product by enrichment purification-liquid chromatography tandem mass spectrometry and application | |
| CN102445507B (en) | Method for determining vinyl content in methyl vinylsiloxane rubber or silicone oil | |
| CN104865332A (en) | Method for rapidly detecting content of multiple organic acid radical ions | |
| CN106226454B (en) | The ion chromatographic method of trace chloro ion in a kind of measure trimethyl gallium | |
| CN104597000A (en) | Hydride generation-atomic florescence spectrometry method for determining trace quantity of antimony in galvanized steel sheet plating | |
| CN110231430A (en) | A kind of ion chromatographic method for chloride content determination in titanium sponge | |
| CN106198767B (en) | The detection method of sulfuric acid content in a kind of tin methane sulfonate system electroplate liquid | |
| CN105675709A (en) | Method for rapidly measuring trace osmium with inductively coupled plasma-massspectrometry | |
| CN103018219A (en) | Application of 4,5-dimethoxyphthalaldehyde in detection of ammonium nitrogen in water and determination method | |
| CN110220856A (en) | The method that Flow Injection Analysis detects chloride ion content in the electrodeposit liquid of electrolytic copper foil | |
| CN106908400B (en) | A kind of total Phosphorus In Soil detection method based on Continuous Flow Analysis instrument | |
| CN102830154A (en) | Method for measuring content of phosphorus in ferrotungsten | |
| CN111351893A (en) | Method for detecting content of guanidine ions in guanidine hydrochloride sample by using ion chromatography | |
| CN110749667A (en) | Analysis and detection method of four neonicotinoid insecticides in water | |
| CN109212062A (en) | A method of with nicotinonitrile and 3- picoline in HPLC detection industrial wastewater | |
| CN112255341A (en) | Method for detecting benzene series in water by negative pressure headspace gas chromatography | |
| CN109507306B (en) | Method for determining acetyl tributyl citrate in water-based adhesive | |
| CN106556669A (en) | A kind of method of content of organic chloride in measure Oilfield Chemicals | |
| CN113030286A (en) | Determination of hexamethyldisilazane content in tris (trimethylsilyl) phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |