CN113063873B - Method for measuring chlorine content in zirconium sponge - Google Patents
Method for measuring chlorine content in zirconium sponge Download PDFInfo
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Abstract
The invention provides a method for measuring chlorine content in zirconium sponge, which comprises the steps of preparing a zirconium sponge sample solution X, preparing a zirconium sponge sample diluted solution Y, activating an H column, preparing a sample on-machine test solution Z and the like, preparing the sample into a solution which can be measured on an ion chromatograph, removing zirconium in the zirconium sponge solution, and avoiding pollution to a chromatographic column; the prepared working curve standard solutions with different chlorine contents can cover the analysis of the conventional chlorine content in zirconium sponge; and (3) respectively testing the standard solution of the working curve and the test liquid of the sample loading machine under the working condition of the determined ion chromatograph, so that the fluoride ions and the chloride ions are completely separated. In peak area and Cl ‑ The standard solution concentration establishes a working curve, and the percentage content of chlorine in the zirconium sponge can be accurately obtained through the chromatographic peak area of the chlorine ions of the measured zirconium sponge sample on-machine test solution, so that the measurement time is saved, and the scientific research and production requirements can be met.
Description
Technical Field
The invention belongs to the technical field of analysis and test, and particularly relates to a method for measuring chlorine content in zirconium sponge.
Background
Titanium alloy is widely applied to the fields of ships, aviation, aerospace, weaponry and the like in terms of excellent performances such as high strength, good corrosion resistance and the like. The titanium alloy components and the production process influence the performance of the titanium alloy, chlorine is an impurity, and also influences the performance of the titanium alloy, such as pollution of the chlorine to a vacuum system during ingot casting, influence on the service life of equipment and the like. The existence of chlorine in the titanium alloy production raw material zirconium sponge is one of factors for introducing chlorine in the titanium alloy. Zirconium sponge is used as a raw material for manufacturing zirconium alloy, as well as for manufacturing bulletproof alloy steel, cladding alloy of uranium fuel in a reactor, and the like. The nuclear grade zirconium sponge is an important raw material for manufacturing nuclear grade zirconium alloy, and belongs to national strategic materials. Chlorine is one of the main factors affecting the purity of zirconium sponge, and the upper limit of the content of chlorine is different for zirconium sponge of different grades.
Therefore, the chlorine content of the sponge zirconium needs to be strictly controlled, the sponge zirconium product standards at home and abroad such as American standard ASTM B494-08 (2014), standard Specification for Primary Zirconium, ASTM B349/349M-16, chinese colored industry standard YS/T397-2015, sponge zirconium made by enterprises and the like have upper limit requirements on the chlorine content of the sponge zirconium, the upper limit requirements on the chlorine content of the sponge zirconium of different grades such as nuclear grade, industrial grade and the like are different, for example, the chlorine in nuclear grade sponge zirconium HZr-01 and HZr-02 is not more than 0.030 percent, 0.080 percent respectively, the chlorine in industrial grade sponge zirconium HZr-1 is not more than 0.130 percent, the chlorine in firearm grade sponge zirconium HQZr-1 is not more than 0.130 percent and the like are stipulated in YS/T397-2015.
The current method standard GB/T13747.16-2017 for measuring chlorine in zirconium sponge, namely a zirconium and zirconium alloy chemical analysis method, prescribes that a silver chloride turbidity method, an ion selective electrode method and the like are adopted, wherein the silver chloride turbidity method uses a plurality of reagents, agNO3 is high in price and has the defects of complex operation and inaccurate quantification, the ion selective electrode method uses a potential value as an endpoint criterion, and a plurality of factors influencing the potential value such as temperature, electrodes, salt bridges, the ionic strength of a solution, the performance of an ion meter and the like are needed, and a great amount of preparation work is needed to obtain calibrated equivalent point potentials. Furthermore, the determination of the 16 th partial chlorine content of the zirconium and zirconium alloy chemical analysis method is carried out in the prior standard GB/T13747.16-2017: the analysis ranges of the silver chloride turbidity method and the ion selective electrode method are respectively 0.0010-0.030 percent and 0.0004-0.020 percent, chlorine with the content of more than 0.03 percent in the sponge zirconium can not be measured, and part of the sponge zirconium with the chlorine content of 0.03-0.130 percent can also be used as nuclear grade sponge zirconium HZr-02, industrial grade sponge zirconium HZr-1 and firearm grade sponge zirconium HQZr-1. Therefore, the existing analysis method technology cannot meet the requirements of modern production on scientific classification of the zirconium sponge and precise control of chemical components of the zirconium sponge.
Ion chromatography is the current method for measuring anions, but is used in the fields of environmental monitoring, foods and the like, and no ion chromatography for measuring the chlorine content in zirconium sponge is currently found. There are a number of problems in introducing ion chromatography into the chlorine content determination in zirconium sponge: zirconium sponge is not easy to dissolve, hydrofluoric acid or aqua regia can be used for treating zirconium into solution, and chloride ions are introduced when aqua regia is used, so that chlorine in the zirconium cannot be measured, and therefore, the zirconium sponge is preferably dissolved by using hydrofluoric acid as a solvent. In the case of the hydrofluoric acid solution of zirconium, the prior filter column such as IC-H-1CC and the like loses activity, and the content of zirconium in the sample solution before and after the filtration by the H column is measured, the content of zirconium is almost the same before and after the filtration, and a large amount of zirconium ions exist in the solution after the filtration. It has been found through experimentation that current filter columns are ineffective for filtering zirconium heavy metals from sample solutions treated with hydrofluoric acid. That is, the heavy metals such as zirconium in the solution cannot be removed after the sample solution treated by hydrofluoric acid is filtered by the existing filtering column, and when the solution filtered by the filtering column enters the chromatograph for analysis, a great amount of heavy metals such as zirconium still existing in the solution can seriously pollute the chromatographic column, so that the chromatographic column cannot be used due to failure, the chromatographic column needs to be replaced, and the price of the chromatographic column is high, so that great waste is caused. Furthermore, fluoride anions in the solution interfere with the measurement of chloride ions, making it impossible to measure chlorine in zirconium sponge by ion chromatography, etc.
In summary, the problems of the ion chromatography method for measuring anions such as chlorine in zirconium sponge at present are as follows: 1) Zirconium in the zirconium sponge hydrofluoric acid solution cannot be removed by filtration of the existing filter column; 2) The fluoride anions in the solution interfere with the determination of chloride ions. The measurement of anions such as chlorine in zirconium sponge by ion chromatography cannot be performed.
Disclosure of Invention
The invention provides a method for measuring the chlorine content in zirconium sponge, which aims to solve the technical problems that the prior method for measuring the chlorine content in zirconium sponge cannot measure the chlorine content of more than 0.03% in zirconium sponge and the like and cannot meet the production requirement, and aims to establish a method for rapidly measuring the chlorine content in zirconium sponge by ion chromatography, wherein the method is wide in analysis range, can analyze the chlorine content of 0.009-3.00%, is high in analysis speed, accurate and reliable in result and can meet the requirements of production and scientific research, and the serious pollution of heavy zirconium metal to chromatographic columns can cause failure of the chromatographic columns and the measurement cannot be carried out due to fluorine interference.
The invention adopts the technical scheme for solving the technical problems that: the method for measuring the chlorine content in the zirconium sponge comprises the following steps:
step one: preparing a chlorine standard solution; preparing a chlorine standard solution A, a chlorine standard solution B, a chlorine standard solution C, a chlorine standard solution D and a chlorine standard solution E respectively;
step two: preparing a working curve standard solution; preparing working curve standard solution blank with 0.00 mu g/mL of chlorine, working curve standard solution a with 0.005-0.008 mu g/mL of chlorine, working curve standard solution b with 0.01-0.03 mu g/mL of chlorine, working curve standard solution c with 0.05-0.08 mu g/mL of chlorine, working curve standard solution d with 0.10-0.25 mu g/mL of chlorine, working curve standard solution e with 0.30-0.40 mu g/mL of chlorine, working curve standard solution f with 0.50-0.60 mu g/mL of chlorine, working curve standard solution g with 0.80-1.00 mu g/mL of chlorine, working curve standard solution h with 1.25-1.50 mu g/mL of chlorine, working curve standard solution i with 2.00-3.00 mu g/mL of chlorine,
step three: preparing a zirconium sponge sample solution X; weighing 0.09 g-0.11 g of zirconium sponge sample in a beaker, adding 0.4-0.6 mL of hydrofluoric acid, flushing the wall of the beaker with water after the zirconium sponge sample is completely dissolved, and transferring the zirconium sponge sample into a 100mL volumetric flask to obtain zirconium sponge sample solution X;
step four: preparing a zirconium sponge sample dilution solution Y; transferring 5.00-10.00 mL of zirconium sponge sample solution X into a 100mL volumetric flask, adding 1-10 mL of 15% -20% strong alkali solution into the volumetric flask, and fixing the volume with water to obtain zirconium sponge sample dilution solution Y;
step five: h column activation; washing the IC-H-1CC filter column with 10-20 mL water at constant speed, and standing for 0.4-0.6H for use;
step six: preparing test liquid Z of a sample loading machine; sucking 5-10 mL of diluted solution Y of the zirconium sponge sample by using an injector, respectively and slowly pushing the diluted solution Y into an activated IC-H-1CC filter column and a Nylon single-spring injector filter, discarding 2.5-3.5 mL before, and filtering 2-mL-7 mL after the previous 2.5-3.5 mL, thus obtaining an on-machine test solution Z of the sample;
step seven: preparing reagent blank solution KB; adding 0.4-0.6 mL of hydrofluoric acid into a 100mL volumetric flask, fixing the volume to 100mL by using water, shaking uniformly, transferring 10mL of the mixture from the volumetric flask to a 100mL volumetric flask KB added with 1-10 mL of strong base solution with the concentration of 15% -20%, and fixing the volume by using water to prepare reagent blank solution KB;
step eight: interference and cancellation; cations in the zirconium sponge sample solution are separated and removed by chemical reaction, filtration and electrolysis, anions such as fluorine are changed in flow rate of the leaching solution, and the retention time of the anions is different from the retention time of chloride ions to be detected by adopting a gradient leaching mode;
step nine: respectively testing a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, a working curve standard solution g, a working curve standard solution h and a working curve standard solution i on an ion chromatograph, and establishing a working curve between the chromatographic peak area of chlorine of the working curve standard solution obtained by the test and the concentration of the working curve standard solution, wherein a linear equation of the method is y= 0.3247x-0.0099;
and step ten, injecting the sample on-machine testing solution Z into an ion chromatograph for testing, and calculating the percentage content of chlorine in the zirconium sponge according to the working curve obtained in the step nine and the chromatographic peak area of the sample on-machine testing solution Z obtained by measurement.
Further, in the first step, the chlorine standard solution A contains 95-105 mug/mL of chlorine, the chlorine standard solution B contains 20-30 mug/mL of chlorine, the chlorine standard solution C contains 8-12 mug/mL of chlorine, the chlorine standard solution D contains 3-7 mug/mL of chlorine, and the chlorine standard solution E contains 0.8-1.2 mug/mL of chlorine.
Further, in the first step, the chlorine standard solution A contains 100 mug/mL of chlorine, the chlorine standard solution B contains 25 mug/mL of chlorine, the chlorine standard solution C contains 10 mug/mL of chlorine, the chlorine standard solution D contains 5 mug/mL of chlorine, and the chlorine standard solution E contains 1 mug/mL of chlorine.
Further, the working parameters of the ion chromatograph are that the column temperature is 28-36 ℃, the pool temperature is 32-36 ℃, the flow rate is 0.8-1.1 mL/min, and the KOH leaching concentration gradient is as follows: 0 to 7.4min,13 to 17mmol/L;7.4 to 12.71min,48 to 52mmol/L;12.7 to 25.0 min,13 to 17mmol/L; the sample injection amount is 23-26 mu L; the operation time is 25min, and the operation mode is self-regeneration electrochemical inhibition.
The beneficial effects of the invention are mainly represented in the following aspects:
1. by adopting the method to treat the zirconium sponge sample, zirconium in the zirconium sponge sample solution can be removed, multiple tests are carried out, and the content test value of zirconium in the test solution Z of the sample after treatment is 0.0047 mug/mL, 0.0011 mug/mL, less than or equal to 0.0010 mug/mL and the like, which are not more than 0.005 mug/mL, so that the pollution of zirconium heavy metal to the chromatographic column is avoided, and the failure of the chromatographic column is avoided;
2. the method is adopted to treat the zirconium sponge sample, so that the ion chromatography determination of chlorine in zirconium sponge can be carried out;
3. the method provided by the invention is used for testing the chlorine in the zirconium sponge sample, so that the percentage of the chlorine in the zirconium sponge can be accurately obtained;
4. the determination method provided by the invention is simple to operate, quick in analysis, accurate in result and easy to master. The method has high accuracy and good application effect. After the working conditions of the ion chromatograph are determined, the working curve standard solution is measured to determine a method linear equation, and then the test solution of the sponge zirconium sample on the machine is measured to calculate the percentage content of chlorine in the sponge zirconium, so that the measuring time is saved, and the requirements of scientific research and production can be met;
5. the correlation coefficient 0.99913 of the invention meets the requirement that the correlation coefficient of the general method is not less than 0.995, and the analysis range of 0.0045-3.00% of the invention is compared with the national standard GB/T13747.16-2017 for determination of the 16 th partial chlorine content of the zirconium and zirconium alloy chemical analysis method: the detection upper limit of 0.0010 to 0.030 percent and 0.0004 to 0.020 percent of silver chloride turbidity method and ion selective electrode method is high, and the method can meet the measurement requirement of the chlorine percentage content in the zirconium sponge;
6. the recovery rate test shows that the determination method has accurate result and feasible method;
7. the invention of the patent plays an important role in controlling the quality of products and the like of manufacturers of sponge zirconium, titanium alloy, zirconium alloy and the like, scientific research institutes, application units and the like, and has very broad application prospect. The patent is applied in our company, and analysis and application are carried out on the sponge zirconium purchased by our company, so that the quality of the developed and produced titanium alloy is guaranteed, and a certain effect is played for quality judgment and management of sponge zirconium and titanium alloy products. The application and implementation of the patent can realize the accurate control of chlorine in the zirconium sponge, ensure the stability of the quality of the zirconium sponge and the quality and performance of the titanium alloy produced by the zirconium sponge, and have great potential benefit;
8. the invention can provide a reference method for producing a new variety of filter columns for filter column manufacturers, and provides reference and convenience for filtering and removing heavy metals in solution treated by hydrofluoric acid.
Detailed Description
The present invention will be described in detail with reference to examples, which give detailed embodiments and specific operation procedures on the premise of the technical solution of the present invention, but the scope of protection of the present invention is not limited to the following examples.
The method for measuring the chlorine content in the zirconium sponge comprises the following steps:
step one: preparing a chlorine standard solution; preparing a chlorine standard solution A, a chlorine standard solution B, a chlorine standard solution C, a chlorine standard solution D and a chlorine standard solution E respectively;
step two: preparing a working curve standard solution; preparing working curve standard solution blank with 0.00 mu g/mL of chlorine, working curve standard solution a with 0.005-0.008 mu g/mL of chlorine, working curve standard solution b with 0.01-0.03 mu g/mL of chlorine, working curve standard solution c with 0.05-0.08 mu g/mL of chlorine, working curve standard solution d with 0.10-0.25 mu g/mL of chlorine, working curve standard solution e with 0.30-0.40 mu g/mL of chlorine, working curve standard solution f with 0.50-0.60 mu g/mL of chlorine, working curve standard solution g with 0.80-1.00 mu g/mL of chlorine, working curve standard solution h with 1.25-1.50 mu g/mL of chlorine, working curve standard solution i with 2.00-3.00 mu g/mL of chlorine,
step three: preparing a zirconium sponge sample solution X; weighing 0.09 g-0.11 g of zirconium sponge sample in a plastic beaker, adding 0.4-0.6 mL of hydrofluoric acid, flushing the wall of the cup with water after the zirconium sponge sample is completely dissolved, transferring the cup into a 100mL plastic volumetric flask, and fixing the volume with water to obtain zirconium sponge sample solution X;
step four: preparing a zirconium sponge sample dilution solution Y; transferring 5.00-10.00 mL of zirconium sponge sample solution X into a 100mL plastic volumetric flask, adding 1-10 mL of strong alkali solution with concentration of 15% -20% into the volumetric flask, and fixing the volume with water to obtain zirconium sponge sample dilution solution Y;
step five: h column activation; washing the IC-H-1CC filter column with 10-20 mL water at constant speed, and standing for 0.4-0.6H for use;
step six: preparing test liquid Z of a sample loading machine; sucking 5-10 mL of diluted solution Y of the zirconium sponge sample by using an injector, respectively and slowly pushing the diluted solution Y into an activated IC-H-1CC filter column and a Nylon single-spring injector filter, discarding 2.5-3.5 mL before, and filtering 2-mL-7 mL after the previous 2.5-3.5 mL, thus obtaining an on-machine test solution Z of the sample;
step seven: preparing reagent blank solution KB; adding 0.4-0.6 mL of hydrofluoric acid into a 100mL plastic volumetric flask, fixing the volume to 100mL by using water, shaking uniformly, transferring 10mL of the mixture from the bottle to a 100mL plastic volumetric flask KB added with 1-10 mL of strong base solution with the concentration of 15% -20%, and fixing the volume by using water to prepare reagent blank solution KB;
step eight: interference and cancellation; cations in the zirconium sponge sample solution are separated and removed by chemical reaction, filtration and electrolysis, anions such as fluorine are changed in flow rate of the leaching solution, and the retention time of the anions is different from the retention time of chloride ions to be detected by adopting a gradient leaching mode;
step nine: respectively testing a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, a working curve standard solution g, a working curve standard solution h and a working curve standard solution i on an ion chromatograph, and establishing a working curve between the chromatographic peak area of chlorine of the working curve standard solution obtained by the test and the concentration of the working curve standard solution, wherein a linear equation of the method is y= 0.3247x-0.0099;
and step ten, injecting the sample on-machine testing solution Z into an ion chromatograph for testing, and calculating the percentage content of chlorine in the zirconium sponge according to the working curve obtained in the step nine and the chromatographic peak area of the sample on-machine testing solution Z obtained by measurement.
Further, in the first step, the chlorine standard solution A contains 95-105 mug/mL of chlorine, the chlorine standard solution B contains 20-30 mug/mL of chlorine, the chlorine standard solution C contains 8-12 mug/mL of chlorine, the chlorine standard solution D contains 3-7 mug/mL of chlorine, and the chlorine standard solution E contains 0.8-1.2 mug/mL of chlorine.
Further, in the first step, the chlorine standard solution A contains 100 mug/mL of chlorine, the chlorine standard solution B contains 25 mug/mL of chlorine, the chlorine standard solution C contains 10 mug/mL of chlorine, the chlorine standard solution D contains 5 mug/mL of chlorine, and the chlorine standard solution E contains 1 mug/mL of chlorine.
Further, the working parameters of the ion chromatograph are that the column temperature is 28-36 ℃, the pool temperature is 32-36 ℃, the flow rate is 0.8-1.1 mL/min, and the KOH leaching concentration gradient is as follows: 0 to 7.4min,13 to 17mmol/L;7.4 to 12.71min,48 to 52mmol/L;12.7 to 25.0 min,13 to 17mmol/L; the sample injection amount is 23-26 mu L; the operation time is 25min, and the operation mode is self-regeneration electrochemical inhibition.
Further, the correlation coefficient of the linear equation in step nine is 0.99913.
Detailed description of the preferred embodiments
According to the invention, firstly, the sample is prepared into a solution which can be measured on an ion chromatograph through the steps of preparing a zirconium sponge sample solution X, preparing a zirconium sponge sample diluted solution Y, activating an H column, preparing a sample on-machine test solution Z and the like, so that the sample cannot pollute the chromatographic column during measurement. And then preparing a series of working curve standard solutions with different chlorine contents by using the chloride ion standard solution, so that the standard solutions can cover the analysis of the conventional chlorine content in the zirconium sponge. And then, respectively testing the standard solution of the working curve and the test solution of the sample loading machine under the working condition of the determined ion chromatograph, so that the fluoride ions and the chloride ions are completely separated. By Cl - And drawing a working curve by taking the concentration of the standard solution as an abscissa and the peak area as an ordinate, and calculating the percentage content of chlorine in the zirconium sponge sample according to the chromatographic peak area of the chloride ions of the measured zirconium sponge sample on-machine test solution, thereby solving the problem that no ion chromatography method for the chlorine in the zirconium sponge exists at home and abroad at present. The invention prepares the reagent blank solution KB and the reagent blank solution KB is preparedMeasuring for multiple times by using an ion chromatograph, and calculating the detection limit and the measurement lower limit of the method by statistics; calculating the relative standard deviation of the method through multiple measurement of the zirconium sponge sample; the recovery of the process was calculated by recovery test. And (5) judging the method according to the detection limit, the lower limit, the relative standard deviation and the recovery rate test result condition of the method.
The method for measuring chlorine content in zirconium sponge includes such steps as preparing standard solution of hydrofluoric acid, alkali and chloride ion, treating specimen, preparing high-purity water, preparing plastic beaker, preparing ion chromatograph with conductivity detector, chromatographic work station, anion analysis column, anion protecting column, anion electrolytic regeneration inhibitor, on-line rejection purifying column, full-automatic eluting liquid generator, H-type pretreatment column, according to the determination method, a chlorine-containing 0.00 mug/mL working curve standard solution blank, a 0.005-0.008 mug/mL working curve standard solution a, a 0.01-0.03 mug/mL working curve standard solution b, a 0.05-0.08 mug/mL working curve standard solution c, a 0.10-0.25 mug/mL working curve standard solution d, a 0.30-0.40 mug/mL working curve standard solution e, a 0.50-0.60 mug/mL working curve standard solution f, a 0.80-1.00 mug/mL working curve standard solution g, a 1.25-1.50 mug/mL working curve standard solution H and a 2.00-3.0 mug/mL working curve standard solution i are prepared by stepwise dilution of the chlorine standard solution, and the chlorine ion chromatographic peak area of the working curve standard solution and the concentration of the working curve standard solution are respectively determined under the working parameters of a determined ion chromatograph. According to the method, through the steps of preparing a zirconium sponge sample solution X, preparing a zirconium sponge sample diluted solution Y, activating an H column, preparing a sample on-machine test solution Z and the like, a solution which can be directly measured by an ion chromatograph is obtained, then the prepared sample on-machine test solution Z is measured, and the ion chromatograph can automatically calculate the percentage content of chlorine in zirconium sponge according to a linear equation of the method; the related processes are as follows:
1. preparation of working Curve Standard solution
Placing 10.00mL of a chlorine standard solution with the concentration of 1000 mug/mL into a volumetric flask with the concentration of 100mL, and adding high-purity water to fix the volume to 100mL to prepare a chlorine standard solution A with the concentration of 100 mug/mL;
5.00mL of the chlorine standard solution with the concentration of 1000 mug/mL is placed in a 100mL volumetric flask, high-purity water is added to fix the volume to 200mL, and a chlorine standard solution B with the concentration of 25 mug/mL is prepared;
10.00mL of the chlorine standard solution A is placed in a 100mL volumetric flask, and high-purity water is added to fix the volume to 100mL to prepare a chlorine standard solution C containing 10 mug/mL of chlorine;
5.00mL of the chlorine standard solution A is placed in a 100mL volumetric flask, and high-purity water is added to fix the volume to 100mL to prepare a chlorine standard solution D containing 5 mug/mL of chlorine;
placing 10.00mL of the chlorine standard solution C into a 100mL volumetric flask, and adding high-purity water to a volume of 100mL to prepare a chlorine standard solution E containing 1 mug/mL of chlorine;
adding high-purity water into a 100mL volumetric flask, and fixing the volume to 100mL to prepare a working curve standard solution blank containing 0.00 mug/mL of chlorine;
adding 0.50-0.80 mL of chlorine standard solution E into a 100mL volumetric flask, and preparing a working curve standard solution a containing 0.005-0.008 mug/mL of chlorine by using high-purity water to reach a volume of 100 mL;
adding 1.00-3.00 mL of chlorine standard solution E into a 100mL volumetric flask, and preparing a working curve standard solution b containing 0.010-0.030 mu g/mL of chlorine by using high-purity water to reach a volume of 100 mL;
adding 5.00-8.00 mL of the chlorine standard solution E into a 100mL volumetric flask, and preparing a working curve standard solution c containing 0.050-0.08 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 2.00-5.00 mL of the chlorine standard solution D into a 100mL volumetric flask, and preparing a working curve standard solution D containing 0.100-0.250 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 3.00-4.00 mL of the chlorine standard solution C into a 100mL volumetric flask, and preparing a working curve standard solution e containing 0.30-0.40 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 5.00-6.00 mL of the chlorine standard solution C into a 100mL volumetric flask, and preparing a working curve standard solution f containing 0.50-0.60 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 8.00-10.00 mL of the chlorine standard solution C into a 100mL volumetric flask, and preparing a working curve standard solution g containing 0.80-1.00 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 5.00-6.00 mL of the chlorine standard solution B into a 100mL volumetric flask, and preparing a working curve standard solution h containing 1.25-1.50 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
adding 2.00-3.00 mL of the chlorine standard solution A into a 100mL volumetric flask, and preparing a working curve standard solution i containing 2.00-3.00 mug/mL of chlorine by using high-purity water to fix the volume to 100 mL;
2. preparation of test solution Z for sample loading machine
1) Preparation of zirconium sponge sample solution X. Weighing 0.09 g-0.11 g (accurate to +/-0.0001 g) of zirconium sponge sample into a 250 ml plastic beaker, adding 0.4 ml-0.6 ml of hydrofluoric acid, flushing the wall of the cup with water after the solution is completely dissolved, transferring into a 100ml plastic volumetric flask, and fixing the volume with water to obtain zirconium sponge sample solution X.
2) And (3) preparing a zirconium sponge sample diluted solution Y. Transferring 5.00-10.00 ml of the zirconium sponge sample solution X into a 100ml plastic volumetric flask, adding 1-10 ml of a strong alkali solution with the concentration of 15% -20% into the volumetric flask, and fixing the volume by water to obtain a zirconium sponge sample dilution solution Y.
3) And H column activation. The IC-H-1CC filter column is washed by 10 to 20 percent mL water at constant speed and is used after being placed for 0.5 hour.
4) And (5) preparing a test solution Z of the sample loading machine. The diluted solution Y of the zirconium sponge sample with the concentration of 5mL to 10mL is sucked by a disposable injector, and is respectively and slowly pushed into an activated IC-H-1CC filter column and a Nylon single spring injector filter with the concentration of 0.22 mu m and 13mm, after about 3 mL is discarded, 2 mL mL to 7mL of the diluted solution Y is left to be filtered in a 15 mL plastic tube, so that the sample loading test solution Z which can be directly measured on an ion chromatograph and does not pollute the chromatographic column during measurement is obtained.
Preparation of reagent blank solution KB
Adding 0.4 mL-0.6 mL of hydrofluoric acid into a 100mL plastic volumetric flask, fixing the volume to 100mL of high-purity water, shaking uniformly, transferring 10mL of the mixture from the bottle to a 100mL plastic volumetric flask KB added with 1-10 mL of strong base solution with the concentration of 15% -20%, and fixing the volume with water to prepare reagent blank solution KB.
4. The working parameters of the ion chromatograph are that the column temperature is 28-36 ℃, the pool temperature is 32-36 ℃, the flow rate is 0.8-1.1 mL/min, and the KOH leaching concentration gradient is as follows: 0 to 7.4min,13 to 17mmol/L;7.4 to 12.71min,48 to 52mmol/L;12.7 to 25.0 min,13 to 17mmol/L; the sample injection amount is 23-26 mu L; the operation time is 25min, and the operation mode is self-regeneration electrochemical inhibition.
Interference and cancellation; the cations in the zirconium sponge sample solution are separated and removed by chemical reaction, filtration and electrolysis, and anions such as fluorine are separated from chloride ions to be detected by changing the flow of the leaching solution and adopting a gradient leaching mode to ensure that the retention time of the anions is different from the retention time of the chloride ions to be detected.
The linear equation of the method, the measurement of the sample, the detection limit of the method and the relative standard deviation; according to the working curve standard solution blank, the working curve standard solution a, the working curve standard solution b, the working curve standard solution c, the working curve standard solution d, the working curve standard solution e, the working curve standard solution f, the working curve standard solution g, the working curve standard solution h and the working curve standard solution i, and the working curve relation between the chlorine chromatographic peak area and the concentration of the working curve standard solution i, a linear equation y= 0.3247x-0.0099 is established, the correlation coefficient of the linear equation is 0.99913, then the on-machine test solution Z of a sample is measured and the chromatographic peak area of the test solution Z is obtained, and the ion chromatograph can automatically calculate the percentage content of chlorine in the sponge zirconium according to the working curve;
performing 10 times of measurement on the reagent blank solution, and multiplying the standard deviation average value of the 10 times of measurement by 3 to obtain a detection limit, wherein the detection limit is 0.0027%; the lower limit of the method measurement was obtained by multiplying the standard deviation average value of 10 measurements by 10, and the lower limit of the measurement was 0.009%.
The average value of chlorine content obtained by 8 times of measurement of the sample loading test solution Z of a certain zirconium sponge sample is 0.1172%, the SD value thereof is 0.0029%, and the relative standard deviation thereof is 2.48%.
Recovery test
And (3) adding a chlorine standard solution into the on-machine test solution of the zirconium sponge sample with the chlorine content detected, and calculating the recovery rate of the chlorine to be 95-110% through a recovery test, wherein the determination method is proved to be completely feasible.
The process provides basic conditions and basic working parameters for measuring the chlorine content in the sponge zirconium, once a method for measuring the chlorine content in the sponge zirconium is established in an ion chromatograph, when the method is tested, the established method for measuring the chlorine content in the sponge zirconium is copied and opened only after the instrument is started and stabilized until the instrument CD is not more than 2 in total, the method comprises an instrument method and a data processing method, the blank working curve standard solution a, the working curve standard solution b, the working curve standard solution c, the working curve standard solution d, the working curve standard solution e, the working curve standard solution f, the working curve standard solution g, the working curve standard solution h and the working curve standard solution i are required to be measured, a new linear equation of a measuring method in a new test state is obtained, then the chromatographic peak area of the chlorine in the test solution Z of the sponge zirconium is obtained by measuring the sample on a machine, the percentage content of the chlorine in the sponge zirconium can be calculated by the ion chromatograph through the linear equation of the measuring method, the parameters and the condition selection are not required, the whole measuring time is saved, the whole measuring time can be saved, the chlorine content can be completed in 340 minutes before the chlorine content can be measured in a small sample and the standard solution can be analyzed, and the sample can be completely analyzed in a small time is required to be measured in a small sample of the test time of the chlorine sample can be obtained, and the sample can be analyzed if the standard can be completely measured in a sample can be measured in a sample has a small standard 8.
It is emphasized that:
(1) The working curve standard solution may be all of a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, a working curve standard solution g, a working curve standard solution h, and a working curve standard solution i, or a combination of at least five working curve standard solutions including the working curve standard solution blank, for example, a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, and a working curve standard solution d, or a combination of five to ten working curve standard solutions such as a working curve standard solution blank, a working curve standard solution b, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, and a working curve standard solution g, so long as the chlorine content in the sample is within the coverage of the working curve.
(2) For the sponge zirconium with the same quality, no matter how much weight is weighed in the range of 0.09 g-0.11 g, the calculated chlorine percentage content is unique by measuring through an ion chromatograph, for example, 0.0900g or 0.1100g of the sponge zirconium with the same quality are weighed simultaneously to respectively prepare two sample upper machine test solutions of the sponge zirconium, and the reference value of the chlorine percentage content in the sample upper machine test solutions of the two sponge zirconium is 0.012 percent.
(3) For sponge zirconium with different qualities, even if the weight values weighed in the range of 0.09 g-0.11 g are equal, the chlorine percentage calculated by an ion chromatograph is unequal, for example, 0.1100g of sponge zirconium with the quality of A or 0.1100g of sponge zirconium with the quality of B are weighed, so that an on-machine test liquid for a sample of sponge zirconium with the quality of A or an on-machine test liquid for a sample of sponge zirconium with the quality of B is prepared, the reference value of the chlorine percentage in the sponge zirconium with the quality of A is 0.026%, and the reference value of the chlorine percentage in the sponge zirconium with the quality of B is 0.048%.
(4) The problem of dilution multiple is to dilute the sample according to different contents of chlorine in the zirconium sponge to different multiples, firstly, the concentration of the chlorine in the sample on-machine test solution is in the concentration range of the standard solution of the working curve and can be detected by an instrument, secondly, the concentration of zirconium in the zirconium sponge sample diluted solution Y is reduced, and the subsequent treatment steps of the zirconium sponge sample on-machine test solution are added to ensure that the zirconium content in the zirconium sponge sample on-machine test solution is lower, so that the pressure of polluting a chromatographic column during on-machine measurement is reduced.
However, the relative standard deviation obtained by repeating the measurement 8 times on the test solution of the zirconium sponge sample was 5% or less.
Therefore, the correlation coefficient 0.99913 of the invention meets the requirement that the correlation coefficient of the general method is not less than 0.995, and the lower measurement limit of 0.009% of the invention meets the measurement requirement of the chlorine percentage content in the zirconium sponge.
From the above analysis, it can be seen that: according to the method, a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, a working curve standard solution g, a working curve standard solution h and a working curve standard solution i are prepared by stepwise dilution of a chlorine standard solution of 1000 mug/mL, the working curve standard solutions are respectively measured under the working condition of a determined ion chromatograph, a working curve is established between the chloride ion chromatographic peak area of the working curve standard solution and the concentration of the chloride ion chromatographic peak area, the working curve standard solution is measured on-machine test solution of a prepared sample of the sponge zirconium, and the ion chromatograph can automatically calculate the percentage content of chlorine in the sponge zirconium according to a linear equation of the method.
The method for measuring the chlorine content in the zirconium sponge disclosed by the invention is used for perfecting the problem of ion chromatography measurement of no chlorine content in the zirconium sponge in domestic and foreign standards, eliminating pollution of zirconium heavy metal to a chromatographic column, avoiding failure of the chromatographic column caused by the pollution, and has the characteristics of simplicity in operation, rapidness in analysis, accurate result, easiness in mastering, high accuracy, good application effect and the like. According to the preparation method of the sample solution X, the preparation of the sample dilution solution Y, the activation of the H column and the preparation method of the sample on-machine test solution Z, zirconium heavy metals can be removed, the pollution to the chromatographic column is avoided, and the failure of the chromatographic column is avoided.
The reagents used in the determination method of the invention mainly comprise hydrofluoric acid, strong alkali, chloridion standard solution and the like, the strong alkali can be potassium hydroxide or sodium hydroxide, the potassium hydroxide is preferentially used in the method, the water used for processing samples and preparing the standard solution is high-purity water, the used instruments and equipment mainly comprise a plastic king beaker, a plastic volumetric flask, an ion chromatograph and the like, and the ion chromatograph is provided with a conductivity detector, a chromatographic workstation, an anion analysis column, an anion protection column, an anion electrolysis regeneration inhibitor, an online rejection purification column, a full-automatic leaching solution generator, an H-shaped pretreatment column and the like.
We analyzed the titanium in the sample solutions of the titanium sponge solutions treated with hydrofluoric acid and nitric acid before and after H-column filtration, and the titanium content was almost the same before and after filtration. The presence of titanium heavy metals can also contaminate the column, rendering it useless. It is known that the conventional H-column is ineffective for heavy metal filtration of a sample solution treated with hydrofluoric acid. The present invention is represented by a method for treating zirconium sponge, and a method for treating titanium sponge or other sample solutions obtained by treating titanium sponge with a solution containing hydrofluoric acid can be referred to as a method for treating zirconium sponge to avoid contamination of a chromatographic column, but the amount of the reagent used is different from that of the present invention, and this is particularly important to note.
The present invention is not limited to the technical scheme and embodiments, but is described in detail with reference to the preferred examples, and those skilled in the art will understand that: modifications may be made to the specific embodiments of the present invention or equivalents may be substituted for part of the technical features thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed. It should also be noted that relational terms are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Claims (4)
1. A method for measuring chlorine content in zirconium sponge is characterized by comprising the following steps: the method comprises the following steps:
step one: preparing a chlorine standard solution; preparing a chlorine standard solution A, a chlorine standard solution B, a chlorine standard solution C, a chlorine standard solution D and a chlorine standard solution E respectively;
step two: preparing a working curve standard solution; preparing working curve standard solution blank with 0.00 mu g/mL of chlorine, working curve standard solution a with 0.005-0.008 mu g/mL of chlorine, working curve standard solution b with 0.01-0.03 mu g/mL of chlorine, working curve standard solution c with 0.05-0.08 mu g/mL of chlorine, working curve standard solution d with 0.10-0.25 mu g/mL of chlorine, working curve standard solution e with 0.30-0.40 mu g/mL of chlorine, working curve standard solution f with 0.50-0.60 mu g/mL of chlorine, working curve standard solution g with 0.80-1.00 mu g/mL of chlorine, working curve standard solution h with 1.25-1.50 mu g/mL of chlorine, working curve standard solution i with 2.00-3.00 mu g/mL of chlorine,
step three: preparing a zirconium sponge sample solution X; weighing 0.09 g-0.11 g of zirconium sponge sample in a beaker, adding 0.4-0.6 mL of hydrofluoric acid, flushing the wall of the beaker with water after the zirconium sponge sample is completely dissolved, and transferring the zirconium sponge sample into a 100mL volumetric flask to obtain zirconium sponge sample solution X;
step four: preparing a zirconium sponge sample dilution solution Y; transferring 5.00-10.00 mL of zirconium sponge sample solution X into a 100mL volumetric flask, adding 1-10 mL of 15% -20% strong alkali solution into the volumetric flask, and fixing the volume with water to obtain zirconium sponge sample dilution solution Y;
step five: h column activation; washing the IC-H-1CC filter column with 10-20 mL water at constant speed, and standing for 0.4-0.6H for use;
step six: preparing test liquid Z of a sample loading machine; sucking 5-10 mL of diluted solution Y of the zirconium sponge sample by using an injector, respectively and slowly pushing the diluted solution Y into an activated IC-H-1CC filter column and a Nylon single-spring injector filter, discarding 2.5-3.5 mL before, and filtering 2-mL-7 mL after the previous 2.5-3.5 mL is discarded, thus obtaining an on-machine test solution Z of the sample;
step seven: preparing reagent blank solution KB; adding 0.4-0.6 mL of hydrofluoric acid into a 100mL volumetric flask, fixing the volume to 100mL by using water, shaking uniformly, transferring 10mL of the mixture from the volumetric flask to a 100mL volumetric flask KB added with 1-10 mL of strong base solution with the concentration of 15% -20%, and fixing the volume by using water to prepare reagent blank solution KB;
step eight: interference and cancellation; the cations in the zirconium sponge sample solution are separated and removed by chemical reaction, filtration and electrolysis, and the fluorine anions are changed in flow rate by changing the leaching solution, so that the retention time of the fluorine anions is different from the retention time of chloride ions to be detected by adopting a gradient leaching mode;
step nine: respectively testing a working curve standard solution blank, a working curve standard solution a, a working curve standard solution b, a working curve standard solution c, a working curve standard solution d, a working curve standard solution e, a working curve standard solution f, a working curve standard solution g, a working curve standard solution h and a working curve standard solution i on an ion chromatograph, and establishing a working curve between the chromatographic peak area of chlorine of the working curve standard solution obtained by the test and the concentration of the working curve standard solution, wherein a linear equation of the method is y= 0.3247x-0.0099;
step ten, injecting the sample on-machine testing solution Z into an ion chromatograph for testing, and calculating the percentage content of chlorine in the zirconium sponge according to the working curve obtained in the step nine and the chromatographic peak area of the sample on-machine testing solution Z obtained by measurement;
the correlation coefficient of the linear equation in the step nine is 0.99913;
performing 10 times of measurement on the reagent blank solution, and multiplying the standard deviation average value of the 10 times of measurement by 3 to obtain a detection limit, wherein the detection limit is 0.0027%; multiplying the standard deviation average value of 10 times to obtain a method lower measurement limit, wherein the method lower measurement limit is 0.009%; the average value of chlorine content obtained by 8 times of measurement of a sample loading test solution Z of a certain zirconium sponge sample is 0.1172%, the SD value is 0.0029%, and the relative standard deviation is 2.48%; and adding a chlorine standard solution into the on-machine test solution of the zirconium sponge sample with the chlorine content detected, and calculating the recovery rate of the chlorine to be 95-110% through a recovery test.
2. The method for measuring the chlorine content in zirconium sponge according to claim 1, wherein the method comprises the following steps: in the first step, the chlorine content of the chlorine standard solution A is 95-105 mug/mL, the chlorine content of the chlorine standard solution B is 20-30 mug/mL, the chlorine content of the chlorine standard solution C is 8-12 mug/mL, the chlorine content of the chlorine standard solution D is 3-7 mug/mL, and the chlorine content of the chlorine standard solution E is 0.8-1.2 mug/mL.
3. The method for measuring the chlorine content in zirconium sponge according to claim 2, wherein the method comprises the following steps: in the first step, the chlorine standard solution A contains 100 mug/mL of chlorine, the chlorine standard solution B contains 25 mug/mL of chlorine, the chlorine standard solution C contains 10 mug/mL of chlorine, the chlorine standard solution D contains 5 mug/mL of chlorine, and the chlorine standard solution E contains 1 mug/mL of chlorine.
4. The method for measuring the chlorine content in zirconium sponge according to claim 1, wherein the method comprises the following steps: the working parameters of the ion chromatograph are that the column temperature is 28-36 ℃, the pool temperature is 32-36 ℃, the flow rate is 0.8-1.1 mL/min, and the KOH leaching concentration gradient is as follows: 0 to 7.4min,13 to 17mmol/L;7.4 to 12.7min,48 to 52mmol/L;12.7 to 25.0 min,13 to 17mmol/L; the sample injection amount is 23-26 mu L; the operation time is 25min, and the operation mode is self-regeneration electrochemical inhibition.
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