CN103293121A - Residual chlorine standard substance, application of residual chlorine standard substance and residual chlorine tester correction or calibration method - Google Patents
Residual chlorine standard substance, application of residual chlorine standard substance and residual chlorine tester correction or calibration method Download PDFInfo
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- CN103293121A CN103293121A CN2013102076814A CN201310207681A CN103293121A CN 103293121 A CN103293121 A CN 103293121A CN 2013102076814 A CN2013102076814 A CN 2013102076814A CN 201310207681 A CN201310207681 A CN 201310207681A CN 103293121 A CN103293121 A CN 103293121A
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Abstract
The invention provides a residual chlorine standard substance. The residual chlorine standard substance comprises the following two series: a free residual chlorine standard substance and a total residual chlorine standard substance, wherein the free residual chlorine standard substance comprises a low-value free residual chlorine standard substance and a high-value free residual chlorine standard substance; the concentration of the low-value free residual chlorine standard substance is 10+/-1.0mg/L; the concentration of the high-value free residual chlorine standard substance is 50+/-5.0mg/L; the total residual chlorine standard substance comprises a low-value total residual chlorine standard substance and a high-value total residual chlorine standard substance; the concentration of the low-value total residual chlorine standard substance is 50+/-1.0mg/L; the concentration of the high-value total residual chlorine standard substance is 500+/-10.0mg/L; a residual chlorine standard solution is prepared by taking an iodine standard solution and chloramine T as a reagent main body according to the required concentration. The invention also provides a residual chlorine standard substance testing method.
Description
Technical field
The present invention relates to the calibrating field of chlorine residual measurement instrument, cover the transmission of quantity value field of metrology and measurement simultaneously, particularly relate to a kind of chlorine residual measurement instrument standard verification solution with broad applicability.
Background technology
The chlorine residual measurement instrument is mainly used in chlorine residue constituent analysis in the various water bodys, and chlorine residue refers to water through chlorination, behind the contact certain hour, remains in the chlorine in the water.Chlorine residue has three kinds of forms: free chlorine residual, chemical combination chlorine residue and total residual chlorine, and wherein free chlorine residual comprises simple substance chlorine, hypochlorous acid and hypochlorite, and the chemical combination chlorine residue comprises monochloro amine, dichlormaine and other chloramines compounds, and total residual chlorine comprises free chlorine residual and chemical combination chlorine residue.As an important step in the water examination quality control, country has strict discharging that clear and definite regulation is arranged to Drinking Water and hospital sewage total residual chlorine.Therefore, chlorine residue is effectively measured, with guarantee people healthy be very significant.
The method of measuring chlorine residue is a lot, and chemical analysis, spectrophotometric method, electrochemical process, residual chlorine sensor method etc. are arranged.Chlorine residual measurement instrument on the market is according to N mostly at present, N-diethyl p-phenylenediamine (DPD) photometry is carried out the instrument that residual chlorine concentration detects, it is a kind of in the optical filtering photolometer, principle is the characteristic absorption spectrum that visible light produced according to material molecule and the principle of law of light absorption (Lambert-Beer's law), the instrument that carries out quantitative test with the method for unknown concentration sample and the comparison of concentration known standard solution.Wherein, portable chlorine residual measurement instrument is simple to operate, easy to carry because of it, is applicable to fast-field evaluation, can satisfy every profession and trade realizes the on-the-spot requirement that detects the chlorine residue index of water quality, so that in time grasp the chlorine residue index of water quality, control water quality in optimum condition, thereby be subjected to user's welcome.
In view of existing chlorine residue instrument quality uneven, and there is not effective chlorine residue standard substance that the instrument testing result is calibrated, accuracy to the instrument testing result is difficult to assessment, causes this index monitoring possible out of control, and the environmentally safe and domestic water sense of security is brought considerable influence.So be badly in need of development chlorine residue standard substance, for the mechanism for monitoring quality control provides foundation, set up chlorine residual measurement instrument magnitude tracing system, effectively ensure urbanite water consumption safety and environment water quality.
In sum, this area lack that a kind of definite value is reliable, stable free chlorine residue standard substance and total residual chlorine standard substance.
Therefore, this area presses for that a kind of definite value of exploitation is reliable, stable free chlorine residue standard substance and total residual chlorine standard substance, can be used to carry out the calibration of chlorine residual measurement instrument, for the magnitude tracing of chlorine residual measurement provides safeguard.
Summary of the invention
First purpose of the present invention is to obtain that a kind of definite value is reliable, stable free chlorine residue standard substance and total residual chlorine standard substance, can be used to carry out the calibration of chlorine residual measurement instrument, for the magnitude tracing of chlorine residual measurement provides safeguard.
Second purpose of the present invention is to obtain a kind ofly to adopt that definite value is reliable, the calibration of chlorine residual measurement instrument or the calibration method of stable free chlorine residue standard substance and total residual chlorine standard substance, it is used for carrying out the calibration of chlorine residual measurement instrument, for the magnitude tracing of chlorine residual measurement provides safeguard.
The 3rd purpose of the present invention is to obtain that a kind of definite value is reliable, the purposes of stable free chlorine residue standard substance and total residual chlorine standard substance, can be used to carry out the calibration of chlorine residual measurement instrument, for the magnitude tracing of chlorine residual measurement provides safeguard.
In a first aspect of the present invention, a kind of chlorine residue standard substance is provided, described chlorine residue standard substance comprises following two series:
Free chlorine residual standard substance, described free chlorine residual standard substance comprise low value free chlorine residual standard substance and high value free chlorine residual standard substance; The concentration of described low value free chlorine residual standard substance is 10 ± 1.0mg/L; The concentration of described high value free chlorine residual standard substance is 50 ± 5.0mg/L;
Total residual chlorine standard substance, described total residual chlorine standard substance comprise low value total residual chlorine standard substance and high value total residual chlorine standard substance; The concentration of described low value total residual chlorine standard substance is: 50 ± 1.0mg/L; The concentration of described high value total residual chlorine standard substance: 500 ± 10.0mg/L;
Described chlorine residue standard solution is to be the reagent main body with iodine standard solution and toluene-sodium-sulfonchloramide, and is formulated according to desired concn.
In an embodiment, it is the reagent main body that the present invention selects national certified reference material for use, is that element body is formulated with the electron level ultrapure water.
In a specific embodiment of the present invention, described chlorine residue standard substance by following two series totally four groups of standard substances form:
Low value is from chlorine residue standard substance: 10 ± 1.0mg/L;
High value free chlorine residual standard substance: 50 ± 5.0mg/L;
Low value total residual chlorine standard substance: 50 ± 1.0mg/L;
High value total residual chlorine standard substance: 500 ± 10.0mg/L.
In an embodiment, the present invention's " chlorine residue standard substance " is free chlorine residual standard substance and two kinds of standard solution series of total residual chlorine standard substance.This series solution is 4 groups, wherein free chlorine residual standard substance (low value): 10mg/L; Free chlorine residual standard substance (high value): 50mg/L; Total residual chlorine standard substance (low value): 50mg/L; Total residual chlorine standard substance (high value): 500mg/L.
In a specific embodiment of the present invention, the concentration of described low value free chlorine residual standard substance is set in 1:(5 ± 1 with the ratio of the concentration of high value free chlorine residual standard substance).
In a specific embodiment of the present invention, described low value total residual chlorine standard substance is set in 1:(10 ± 2 with the ratio of the concentration of high value total residual chlorine standard substance).
In a specific embodiment of the present invention, described free chlorine residual standard substance is formulated by the iodometric titration standard substance.
In a specific embodiment of the present invention, the described standard solution of described total residual chlorine standard substance wherein is formulated by toluene-sodium-sulfonchloramide reagent.
In a specific embodiment of the present invention, the solvent of described standard solution is the electron level ultrapure water.
A second aspect of the present invention provides a kind of employing calibration of chlorine residual measurement instrument or the calibration method of chlorine residue standard substance as described in the present invention.
In a specific embodiment of the present invention, described chlorine residual measurement instrument calibration or calibration method are applicable to the different wave length detection system, comprise that wavelength is the wavelength detection system of 248nm, 420～440nm, 510～530nm.
In an embodiment, described iodometric titration standard substance and toluene-sodium-sulfonchloramide reagent can with N, developers such as N-diethyl p-phenylenediamine, o-tolidine, tetramethyl benzidine reactions; More specifically, the calibration of the chlorine residual measurement instrument of described chlorine residue standard substance or calibration method are applicable to the different wave length detection system, comprise that wavelength is the wavelength detection system of 248nm, 420～440nm, 510～530nm.
A third aspect of the present invention provides a kind of purposes of chlorine residue standard substance as claimed in claim 1, it is characterized in that, the every evaluation of indexes of instrument when being used for the calibration of chlorine residual measurement instrument or calibrating.
Embodiment
Therefore, the present invention is intended to by a series of tests, develops that definite value is reliable, stable free chlorine residue standard substance and total residual chlorine standard substance, can be used to carry out the calibration of chlorine residual measurement instrument, for the magnitude tracing of chlorine residual measurement provides safeguard.
Among the present invention, term " contains " or the various compositions of " comprising " expression can be applied in potpourri of the present invention or the composition together.Therefore, term " mainly by ... form " and " by ... composition " be included in that term " contains " or in " comprising ".
Below describe in detail to various aspects of the present invention:
The chlorine residue standard substance
In a first aspect of the present invention, a kind of chlorine residue standard substance is provided, described chlorine residue standard substance comprises following two series:
Free chlorine residual standard substance, described free chlorine residual standard substance comprise low value free chlorine residual standard substance and high value free chlorine residual standard substance; The concentration of described low value free chlorine residual standard substance is 10 ± 1.0mg/L; The concentration of described high value free chlorine residual standard substance is 50 ± 5.0mg/L;
Total residual chlorine standard substance, described total residual chlorine standard substance comprise low value total residual chlorine standard substance and high value total residual chlorine standard substance; The concentration of described low value total residual chlorine standard substance is: 50 ± 1.0mg/L; The concentration of described high value total residual chlorine standard substance: 500 ± 10.0mg/L;
Described chlorine residue standard solution is to be the reagent main body with iodine standard solution and toluene-sodium-sulfonchloramide, and is formulated according to desired concn.
The inventor finds, can be used for the chlorine residual measurement instrument to calibrate/the every evaluation of indexes of instrument when examining and determine; Chlorine residue standard substance of the present invention is owing to adopt titrimetry to carry out definite value, so definite value is reliable, stable, for the magnitude tracing of chlorine residual measurement provides safeguard; Since the iodometric titration standard substance that adopts and toluene-sodium-sulfonchloramide reagent can with N, the reaction of developers such as N-diethyl p-phenylenediamine, o-tolidine, tetramethyl benzidine makes that the different wave length detection system can applicable wavelengths be 248nm, 420～440nm, 510～530nm.
Described magnitude tracing and stability are please referring to embodiment.
In an embodiment, it is the reagent main body that the present invention selects national certified reference material for use, is that element body is formulated with the electron level ultrapure water.
In a specific embodiment of the present invention, described chlorine residue standard substance by following two series totally four groups of standard substances form:
Low value is from chlorine residue standard substance: 10 ± 1.0mg/L;
High value free chlorine residual standard substance: 50 ± 5.0mg/L;
Low value total residual chlorine standard substance: 50 ± 1.0mg/L;
High value total residual chlorine standard substance: 500 ± 10.0mg/L.
In an embodiment, the present invention's " chlorine residue standard substance " is free chlorine residual standard substance and two kinds of standard solution series of total residual chlorine standard substance.This series solution is 4 groups, wherein free chlorine residual standard substance (low value): 10mg/L; Free chlorine residual standard substance (high value): 50mg/L; Total residual chlorine standard substance (low value): 50mg/L; Total residual chlorine standard substance (high value): 500mg/L.
In a specific embodiment of the present invention, the concentration of described low value free chlorine residual standard substance is set in 1:(5 ± 1 with the ratio of the concentration of high value free chlorine residual standard substance).
In a specific embodiment of the present invention, described low value total residual chlorine standard substance is set in 1:(10 ± 2 with the ratio of the concentration of high value total residual chlorine standard substance).
In a specific embodiment of the present invention, described free chlorine residual standard substance is formulated by the iodometric titration standard substance.
In a specific embodiment of the present invention, the described standard solution of described total residual chlorine standard substance wherein is formulated by toluene-sodium-sulfonchloramide reagent.
In a specific embodiment of the present invention, the solvent of described standard solution is the electron level ultrapure water.
Compound method of the present invention is as follows:
1. free chlorine residual standard substance: adopt A level transfer pipet and liquid-transfering gun, the iodometric titration standard substance of measuring certain volume places volumetric flask, and uses the ultrapure water constant volume.
2. total residual chlorine standard substance: adopt electronic balance to take by weighing the compound of the corresponding weight of certain component respectively, place beaker and fully dissolve with ultrapure water, be transferred in the volumetric flask, blend even allotment and dilution with ultrapure water.
The calibration of chlorine residual measurement instrument or calibration method
A second aspect of the present invention provides a kind of employing calibration of chlorine residual measurement instrument or the calibration method of chlorine residue standard substance as described in the present invention.
In a specific embodiment of the present invention, described chlorine residual measurement instrument calibration or calibration method are applicable to the different wave length detection system, comprise that wavelength is the wavelength detection system of 248nm, 420～440nm, 510～530nm.
In an embodiment, described iodometric titration standard substance and toluene-sodium-sulfonchloramide reagent can with N, developers such as N-diethyl p-phenylenediamine, o-tolidine, tetramethyl benzidine reactions; More specifically, the calibration of the chlorine residual measurement instrument of described chlorine residue standard substance or calibration method are applicable to the different wave length detection system, comprise that wavelength is the wavelength detection system of 248nm, 420～440nm, 510～530nm.
A third aspect of the present invention provides a kind of purposes of chlorine residue standard substance as claimed in claim 1, it is characterized in that, the every evaluation of indexes of instrument when being used for the calibration of chlorine residual measurement instrument or calibrating.
The inventor finds, can be used for the chlorine residual measurement instrument to calibrate/the every evaluation of indexes of instrument when examining and determine; Chlorine residue standard substance of the present invention is owing to adopt titrimetry to carry out definite value, so definite value is reliable, stable, for the magnitude tracing of chlorine residual measurement provides safeguard; Since the iodometric titration standard substance that adopts and toluene-sodium-sulfonchloramide reagent can with N, the reaction of developers such as N-diethyl p-phenylenediamine, o-tolidine, tetramethyl benzidine makes that the different wave length detection system can applicable wavelengths be 248nm, 420～440nm, 510～530nm.
Preferred forms of the present invention
The present invention's " chlorine residue standard substance " is free chlorine residual standard substance and two kinds of standard solution series of total residual chlorine standard substance, is mainly used in portable chlorine residual measurement instrument and calibrates/the every evaluation of indexes of instrument when examining and determine.This series solution is 4 groups, wherein free chlorine residual standard substance (low value): 10mg/L; Free chlorine residual standard substance (high value): 50mg/L; Total residual chlorine standard substance (low value): 50mg/L; Total residual chlorine standard substance (high value): 500mg/L.
Compound method of the present invention is as follows:
3. free chlorine residual standard substance: adopt A level transfer pipet and liquid-transfering gun, the iodometric titration standard substance of measuring certain volume places the 1L volumetric flask, and is settled to 1L with ultrapure water.
4. total residual chlorine standard substance: adopt 100,000/ electronic balance take by weighing the compound of the corresponding weight of certain component respectively, place beaker and fully dissolve with ultrapure water, be transferred in the 1L volumetric flask, blend even allotment and be diluted to 1L with ultrapure water.
Preparing process of the present invention is simple, and good stability is widely applicable, can be widely used at present at the portable chlorine residual measurement instrument with various main flow models.
Technological breakthrough of the present invention is as follows:
1. research chlorine residual measurement instrument target detection thing filters out suitable agent prescription, can both be effective in the different wave length detection system, guarantee to detect the general applicability of solution;
2. realizing on the general applicability basis of solution formula to each detection system, choose certified reference material preparing standard solution series, adopt the valued methods of titration, guaranteed the accuracy of standard solution value, also provide the magnitude tracing material for the associated sample definite value simultaneously.
Specify as nothing, various raw materials of the present invention all can obtain by commercially available; Or prepare according to the conventional method of this area.Unless otherwise defined or explanation, the meaning that all specialties used herein are familiar with scientific words and those skilled in the art is identical.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standard, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight portion, and all number percents are weight percentage, and described polymer molecular weight is number-average molecular weight.
Unless otherwise defined or explanation, the meaning that all specialties used herein are familiar with scientific words and those skilled in the art is identical.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment
1) free chlorine residual standard substance (low value) the 0.1mol/L iodometric titration standard substance that adopts A level transfer pipet and liquid-transfering gun to pipette 2.3ml places volumetric flask, is settled to 1L with ultrapure water.
2) free chlorine residual standard substance (high value) employing A level transfer pipet and the liquid-transfering gun 0.1mol/L iodometric titration standard substance that pipettes 23ml places volumetric flask, is settled to 1L with ultrapure water.
3) total residual chlorine standard substance (low value) adopt 100,000/ electronic balance take by weighing toluene-sodium-sulfonchloramide reagent 0.406g and place beaker, fully dissolve with ultrapure water, shift and put in the 1L volumetric flask, blend even allotment and be diluted to 1L with ultrapure water.
4) total residual chlorine standard substance (high value) adopt 100,000/ electronic balance take by weighing toluene-sodium-sulfonchloramide reagent 4.06g and place beaker, fully dissolve with ultrapure water, transfer is put in the 1L volumetric flask, blends even allotment and is diluted to 1L with ultrapure water.
Free chlorine residual standard substance (low value) adopts the method for titration to carry out definite value, the concrete operations step is as follows: randomly draw sample, open ampoule bottle, accurately measure sample to beaker with A level 15ml transfer pipet, add an amount of distilled water, select the potentiometric titrimeter through assay approval for use, with the sodium thiosulfate standard solution titration that is diluted to 0.001mol/L to terminal, record the volume number of used sodium thiosulfate, be calculated as follows the content of free chlorine residual standard substance
In the formula:
The used volume number of sodium thiosulfate standard solution, ml;
V
ClThe volume number that the free chlorine residual standard substance is used, ml;
Free chlorine residual standard substance (high value) valued methods is the same, and just the volume number of sample sampling is 10ml.
Total residual chlorine standard substance (low value) adopts the method for titration to carry out definite value, the concrete operations step is as follows: randomly draw sample, open ampoule bottle, accurately measure sample to iodine flask with A level 15ml transfer pipet, add an amount of distilled water, add 2ml glacial acetic acid solution mixing again after adding the dissolving of 1g potassium iodide reagents, after in the dark placing 2min, select A level 50ml buret for use, with the sodium thiosulfate standard solution titration that is diluted to 0.001mol/L, add the 1ml0.1% starch indicator when closing on terminal point, it is colourless to terminal to continue titration, record the volume number of used sodium thiosulfate, calculate the content of total residual chlorine standard substance by formula 5-1.
The method of total residual chlorine standard substance (high value) titration is the same, and used standard solution is the 0.01mol/L sodium thiosulfate standard solution when being titration.
Performance embodiment
According to the iodimetric titration among the GB/T5750.11-2006 " the drinking water standard method of inspection ", adopt potentiometric titrimeter and A level buret that 4 kinds of standard substances in the example 1 are carried out definite value, testing result see the following form (mg/L):
After these 4 kinds of standard substances dilution certain multiple, carry out definite value with the ferrous sulphate titrimetry, testing result see the following form (mg/L):
The data of these two kinds of method definite values are compared, the results are shown in following table
Above form as can be known, these 4 kinds of standard substance definite value results are uniform and stable, the measurement result accurate and effective.
Practical approach of the present invention is with reference to prior art.
The above only is preferred embodiment of the present invention, be not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if it is defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a chlorine residue standard substance is characterized in that, described chlorine residue standard substance comprises following two series:
Free chlorine residual standard substance, described free chlorine residual standard substance comprise low value free chlorine residual standard substance and high value free chlorine residual standard substance; The concentration of described low value free chlorine residual standard substance is 10 ± 1.0mg/L; The concentration of described high value free chlorine residual standard substance is 50 ± 5.0mg/L;
Total residual chlorine standard substance, described total residual chlorine standard substance comprise low value total residual chlorine standard substance and high value total residual chlorine standard substance; The concentration of described low value total residual chlorine standard substance is: 50 ± 1.0mg/L; The concentration of described high value total residual chlorine standard substance: 500 ± 10.0mg/L;
Described chlorine residue standard solution is to be the reagent main body with iodine standard solution and toluene-sodium-sulfonchloramide, and is formulated according to desired concn.
2. chlorine residue standard substance as claimed in claim 1 is characterized in that, the concentration of described low value free chlorine residual standard substance is set in 1:(5 ± 1 with the ratio of the concentration of high value free chlorine residual standard substance).
3. chlorine residue standard substance as claimed in claim 1 is characterized in that, described low value total residual chlorine standard substance is set in 1:(10 ± 2 with the ratio of the concentration of high value total residual chlorine standard substance).
4. chlorine residue standard substance as claimed in claim 1 is characterized in that, described chlorine residue standard substance by following two series totally four groups of standard substances form:
Low value is from chlorine residue standard substance: 10 ± 1.0mg/L;
High value free chlorine residual standard substance: 50 ± 5.0mg/L;
Low value total residual chlorine standard substance: 50 ± 1.0mg/L;
High value total residual chlorine standard substance: 500 ± 10.0mg/L.
5. chlorine residue standard substance as claimed in claim 1 is characterized in that, described free chlorine residual standard substance wherein is formulated by the iodometric titration standard substance.
6. chlorine residue standard substance as claimed in claim 1 is characterized in that, the described standard solution of described total residual chlorine standard substance wherein is formulated by toluene-sodium-sulfonchloramide reagent.
7. chlorine residue standard substance as claimed in claim 1 is characterized in that, the solvent of described each standard solution is the electron level ultrapure water.
8. one kind is adopted the chlorine residual measurement instrument of chlorine residue standard substance as claimed in claim 1 to calibrate or calibration method.
9. chlorine residual measurement instrument as claimed in claim 8 is calibrated or calibration method, it is characterized in that, described chlorine residual measurement instrument calibration or calibration method are applicable to the different wave length detection system, comprise that wavelength is the wavelength detection system of 248nm, 420～440nm, 510～530nm.
10. the purposes of a chlorine residue standard substance as claimed in claim 1 is characterized in that, the every evaluation of indexes of instrument when being used for the calibration of chlorine residual measurement instrument or calibrating.
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| CN108351337A (en) * | 2015-10-30 | 2018-07-31 | 哈希公司 | The reference substance of stable storing for the analysis of aqueous chlorine |
| CN105445265A (en) * | 2015-12-03 | 2016-03-30 | 上海仪电科学仪器股份有限公司 | Method for preparing permanent residual chlorine standard colorimetric serial solution |
| CN105445265B (en) * | 2015-12-03 | 2018-06-29 | 上海仪电科学仪器股份有限公司 | The preparation method of permanent chlorine residue standard colorimetric serial solution |
| CN110286196A (en) * | 2019-07-24 | 2019-09-27 | 浙江师范大学 | A method of with quick, Accurate Determining drinking water chlorine residue on site |
| CN112946024A (en) * | 2021-01-27 | 2021-06-11 | 宁波水表(集团)股份有限公司 | Method for testing measurement characteristics of residual chlorine sensor |
| CN112946024B (en) * | 2021-01-27 | 2023-09-15 | 宁波水表(集团)股份有限公司 | Method for checking measurement characteristics of residual chlorine sensor |
| CN115436130A (en) * | 2022-09-02 | 2022-12-06 | 中国计量科学研究院 | Standard substance for simulating free residual chlorine and preparation method thereof |
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| CN103293121B (en) | 2015-12-23 |
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