CN108152343B - Iodine-containing hydriodic acid concentration analysis equipment and method - Google Patents
Iodine-containing hydriodic acid concentration analysis equipment and method Download PDFInfo
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- CN108152343B CN108152343B CN201711124392.2A CN201711124392A CN108152343B CN 108152343 B CN108152343 B CN 108152343B CN 201711124392 A CN201711124392 A CN 201711124392A CN 108152343 B CN108152343 B CN 108152343B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Abstract
A concentration analysis device and a method for iodine-containing hydriodic acid belong to the technical field of electrochemistry and analytical chemistry. The equipment comprises a computer, a hydrogen ion indicating electrode, an oxidation-reduction potential electrode, a temperature sensor, a potentiometer, a measuring pool, a liquid level meter, a KI diluent storage tank, a KCl electrode soak solution storage tank, a waste liquid tank, a pump and pipelines. When the concentration of the iodine-containing hydriodic acid feed liquid is measured, the feed liquid to be measured and KI diluent with a specific multiple are input into a measuring pool, and the concentration of the iodine-containing hydriodic acid feed liquid can be rapidly calculated with the aid of a computer according to a temperature value measured by a temperature sensor and voltage values measured by a hydrogen ion indicating electrode and an oxidation-reduction potential electrode. The method well solves the problems of complicated sampling and measuring processes, time-consuming operation, incapability of monitoring in time and the like in the conventional measurement, can quickly and accurately measure the concentration of the iodine-containing hydriodic acid feed liquid in the container and the pipeline, and is favorable for controlling the related production process.
Description
Technical Field
The invention relates to iodine-containing hydriodic acid (namely hydrogen iodide-iodine-water ternary solution, HI-I)2-H2O) concentration analysis equipment and method, belonging to the technical field of electrochemistry and analytical chemistry.
Background
Iodine-containing hydriodic acid feed liquid (i.e. hydrogen iodide-iodine-water ternary solution, HI-I)2-H2O), is used in daily laboratory analysis, a thermochemical iodine-sulfur cycle water-splitting hydrogen production process and a hydroiodic acid production process. Taking the thermochemical iodine-sulfur cycle water decomposition hydrogen production process (iodine-sulfur cycle for short) as an example, the process relies on hydroiodic acid generated by the Bunsen reaction to form HI-I due to the addition of excessive iodine2-H2O phase, accurately determining HI-I2-H2The concentration of each component in O is very important for the research of related processes and even for the control of field process flows.
HI-I2-H2O has a strong volatility and a strong corrosiveness, especially under the operation conditions of heating and pressurizing. It is thought that the liquid material is very difficult to be in the pipeline and container of the actual production lineAnd manually sampling and analyzing. For the above reasons, it is desirable to address HI-I2-H2O find a suitable concentration analysis method.
Currently, conventional HI-I2-H2The O concentration analysis method is a titration method, which is mostly manually completed in a potentiometric titration mode or completed by using an automatic titrator, in particular, the acid-base titration method is used for determining the HI concentration, and the sodium thiosulfate solution titration method, i.e. an iodometry method is used for determining the I concentration2So that HI-I is obtained2-H2Specific component and content of O (the remaining one component, i.e. H)2The content of O can be obtained by material balance calculation), wherein the acid-base titration method generally uses a hydrogen ion indicating electrode (or a hydrogen ion selective electrode and a pH electrode) to indicate a titration end point; iodometric titration of I2In this case, an oxidation-reduction potential electrode is used as an indicator electrode. Although the titration method has the advantages of small sample consumption, a series of procedures such as sampling, sample weighing, sample dilution and titration are long in time consumption. And due to I in the material-、I2Due to the existence of (I), the accuracy of the titration method is difficult to guarantee because of2/I-The standard potential of the redox couple is neither high nor low, I2Can be reduced by moderately strong reducing agents as oxidizing agents, I-The reagent can also be used as a reducing agent and oxidized by a medium-strength or strong oxidizing agent, so that factors such as the pH value of the material to be detected and oxygen in the air greatly interfere the titration process, and the repeatability is poor. In addition, the titration method requires the preparation, precise calibration and reasonable storage of the titration solution in advance to obtain satisfactory results. In conclusion, the currently widely adopted titration method has the defects of complex operation, time-consuming process, poor repeatability and the like.
According to the Gibbs phase law, under the condition of thermodynamic equilibrium, the relationship among the component number, the phase number and the degree of freedom of the system is as follows:
F＝C-P+2
in the formula: the degree of freedom of the F-system; c-group number of system; p-number of phases in the selected system; and "2" in the formula represents two factors of pressure and temperature.
The number of degrees of freedom F is the number of factors (independent variables such as temperature, pressure, density, age, etc.) that can be independently changed without changing the number of phases when the system is in an equilibrium state. For HI-I2-H2O is a three-component system, under normal pressure,
f ═ C (3 components) -P (1 phase) +1 (given pressure, e.g. under normal pressure, this term is 1) ═ 3.
The degree of freedom F is 3, indicating: in addition to ascertaining the temperature of the solution, only the HI-I is determined2-H2The 2 independently variable factors (i.e., independent variables) of the O system, all physicochemical properties of the system (including, of course, its composition and concentration) are defined values. Thus, in addition to the acquisition temperature, 2 independent variables that are easier to acquire can be selected from which to determine HI-I2-H2Concentration data for O samples.
Chinese patent document (ZL201210517847.8) states that: at normal pressure and fixed temperature, HI-I2-H2O system has only 2 degrees of freedom, and 2 independent variables which are easy to collect can be selected and used for determining HI-I2-H2Concentration data for O samples. Based on the above principle, the Chinese patent document (ZL201210517847.8) discloses an analysis method of iodine-containing hydriodic acid, which adopts a density value and a cell voltage value when flowing through a constant current electrolysis-electrodialysis cell as measurement parameters, and calculates HI-I to be measured with the aid of a computer2-H2The concentration of O. Chinese patent document ZL201210518434.1 provides a container containing iodine hydroiodic acid, which can display the concentration of the feed liquid on line by using the method. The method and the container have a plurality of limitations on the premise of fixed temperature, and HI-I to be measured2-H2The O sample needs to be accurately adjusted in temperature, and accurate results can be obtained when the temperature required by the measuring method is reached. In addition, the electrolytic-electrodialysis cell adopted by the measuring method is not standard equipment, the electrode distance is changed due to the deformation of the gasket of the electrolytic-electrodialysis cell caused by temperature change, material fatigue and the like in the using process, and the cell voltage is strongly related to the electrode distance and is tinyThe change of the inter-polar distance can cause the collected cell voltage to generate great fluctuation, and finally, great measurement errors are caused.
As described above, the hydrogen ion indicating electrode and the oxidation-reduction potential electrode have been used as the indicating electrode for measuring the concentration of iodine-containing hydriodic acid by the titration method, but the workers and researchers have not recognized that: the electrode potentials measured by the hydrogen ion indicating electrode and the oxidation-reduction potential electrode are respectively related to the hydrogen ion concentration and the overall oxidation-reduction potential of the solution, are independent variables closely related to the concentration of the solution, and can be 3 independent variables for determining the concentration of the iodine-containing hydriodic acid solution under normal pressure (or other determined pressure) together with the temperature value. In addition, most of the hydrogen ion indicating electrodes and oxidation-reduction potential electrodes currently supplied in the market have limited measuring range and are used for HI and I2The iodine-containing hydriodic acid solution with too high concentration cannot be directly used for accurately measuring the potential. HI and I of iodine-containing hydriodic acid system in iodine-sulfur cyclic hydrogen production process2The concentration of (A) is often more than 3mol/L, which exceeds the application range of the electrode, and the electrode can be damaged even after being soaked for a long time. This is also the reason why the electrode cannot be directly applied to the concentration determination of iodine-containing hydriodic acid solution.
Disclosure of Invention
The invention aims to provide a device and a method for analyzing the concentration of iodine-containing hydriodic acid, which can well solve the problems of complicated sampling and measuring processes, time-consuming operation, incapability of monitoring in time and the like in conventional measurement, and can quickly and accurately measure the concentration of the iodine-containing hydriodic acid feed liquid in a container and a pipeline, thereby being beneficial to the control of related production processes.
The technical scheme of the invention is as follows:
the utility model provides an iodine-containing hydriodic acid's concentration analytical equipment which characterized in that: the device comprises a computer, a hydrogen ion indicating electrode, an oxidation-reduction potential electrode, a temperature sensor, a potentiometer, a measuring pool, a KI diluent storage tank, a KCl electrode soak storage tank, a waste liquid tank and a pump; the pump comprises a liquid pump of the material to be measured, a KI diluent pump, a KCl electrode soaking liquid pump and a waste liquid pump; the measuring pool is connected with a liquid storage tank to be measured, a conveying pipeline or a tower in the process equipment through a liquid pump and a pipeline of the liquid to be measured; the KI diluent storage tank is connected with the measuring tank through a KI diluent pump and a pipeline; the KCl electrode soaking solution storage tank is connected with the measuring tank through a KCl electrode soaking solution pump and a pipeline; the measuring tank is connected with the waste liquid tank through a pipeline and a waste liquid pump; a hydrogen ion indicating electrode, an oxidation-reduction potential electrode and a temperature sensor are arranged in the measuring pool, and the hydrogen ion indicating electrode and the oxidation-reduction potential electrode are connected with the potentiometer through leads; the potentiometer and the temperature sensor are respectively connected with the computer through signal wires.
Preferably, the temperature sensor can be a free-standing sensor, and can also be arranged in a hydrogen ion indicating electrode or an oxidation-reduction potential electrode.
In the technical scheme, the measuring tank, the KI diluent storage tank, the liquid pump of the material to be measured, the KI diluent pump, the KCl electrode soaking liquid pump, the waste liquid pump and the pipeline of the connecting pump are provided with temperature control and heat preservation facilities.
Another feature of the invention is: the material liquid pump to be detected, the KI diluent liquid pump, the KCl electrode soaking liquid pump and the waste liquid pump are connected with the computer through control lines.
Yet another feature of the invention is: and a liquid level meter is arranged in the measuring tank and is connected with a computer through a control circuit.
The invention provides a method for analyzing the concentration of iodine-containing hydriodic acid, which is characterized by comprising the following steps of:
1) starting a waste liquid pump, emptying the measuring tank, enabling the discharge to flow into a waste liquid tank, and then closing the waste liquid pump to stop a material flow pipeline between the measuring tank and the waste liquid tank;
2) starting a liquid pump of the material to be measured, conveying 0.1-500 mL of iodine-containing hydriodic acid material liquid to be measured into a measuring pool from a material liquid storage tank, a conveying pipeline or a tower to be measured, and then closing the liquid pump of the material to be measured to stop a material flow pipeline between the material liquid storage tank, the conveying pipeline or the tower to be measured and the measuring pool;
3) starting a KI diluent pump, inputting KI diluent into a measuring pool from a KI diluent storage tank, and then closing the KI diluent pump to stop a material flow pipeline between the KI diluent storage tank and the measuring pool; the concentration of the KI diluent is 0.1-3 mol/L, and the delivery volume is 0.1-1000 mL;
4) the potentiometer measures two groups of potential values u of the solution in the measuring cell through a hydrogen ion indicating electrode and an oxidation-reduction potential electrode respectively1And u2Measuring the temperature t of the solution in the measuring cell by the temperature sensor, and combining the two groups of potential values u1And u2 ，The temperature value t is transmitted to a computer, and the computer calculates the concentration of the discharged liquid by utilizing the stored calculation software and displays the concentration;
the calculation software performs calculation according to the following equation set:
u1＝f1(t,cHI,cI2)
u2＝f2(t,cHI,cI2)
equation f1(t,cHI,cI2) Is t, cHIAnd cI2Three variable pairs u1Mathematical expression of (a), (b), f)2(t,cHI,cI2) Is t, cHIAnd cI2Three variable pairs u2A mathematical expression of (a), wherein cHIIs the concentration of HI in the iodine-containing hydriodic acid feed liquid, cI2Is I2T is the temperature value of the solution in the measuring cell;
combining the above two equations, and determining t and u1And u2Namely, the concentration data c of the solution in the measuring cell is calculatedHIAnd cHI(ii) a Then, inversely calculating the concentration data of the original iodine-containing hydriodic acid feed liquid to be detected according to the volume ratio of the KI diluent to the original iodine-containing hydriodic acid feed liquid to be detected;
5) starting a waste liquid pump to empty the material liquid in the measuring tank, sending the discharged material liquid to a waste liquid tank, and then closing the waste liquid pump to stop a material flow pipeline between the measuring tank and the waste liquid tank;
6) starting a KI diluent pump, inputting KI diluent into a measuring pool from a KI diluent storage tank, and closing the KI diluent pump to stop a material flow pipeline between the KI diluent storage tank and the measuring pool; kThe conveying volume of the diluent is 5 to 1000 mL; opening a waste liquid pump to empty the measuring tank, sending the discharged material liquid to a waste liquid tank, then closing the waste liquid pump,flow between measuring cell and waste tank The pipeline is cut off;
7) and (3) starting a KCl electrode soaking liquid pump, inputting the KCl electrode soaking liquid into the measuring pool from a KCl electrode soaking liquid storage tank, closing the KCl electrode soaking liquid pump, and stopping a logistics pipeline between the KCl electrode soaking liquid storage tank and the measuring pool, wherein the concentration of the KCl electrode soaking liquid is 0.1-4 mol/L.
The invention has the following advantages and prominent technical effects: the method adopts the temperature of the feed liquid and the potential values measured by the hydrogen ion indicating electrode and the oxidation-reduction potential electrode to calculate the concentration information of the iodine-containing hydriodic acid, has convenient and quick data acquisition and accurate analysis result, and can overcome the defects of complicated sampling-analysis operation, time-consuming process and the like of the conventional titration analysis method. The temperature sensor, the hydrogen ion indicating electrode and the oxidation-reduction potential electrode adopted by the equipment and the method can conveniently select mature commercial standard products, and the equipment is convenient to debug and maintain; simultaneously this application is through the use of measuring pump, KI diluent, KCl electrode soak, carries out the ration to the feed liquid that awaits measuring and dilutes to in time wash measuring the cell body, guarantee that the electrode is in good operating condition, solved the suitability problem of hydrogen ion indicating electrode, oxidation reduction potential electrode when determining iodine-containing hydriodic acid solution concentration well.
Drawings
Fig. 1 is a schematic structural principle diagram of an embodiment of the analytical equipment for iodine-containing hydriodic acid concentration provided by the invention.
In the figure: 1-a computer; 2-hydrogen ion indicating electrode; 3-an oxidation-reduction potential electrode; 4-a temperature sensor; 5-a potentiometer; 6-a measuring cell; 7a-KI diluent storage tank; a 7b-KCl electrode soak solution storage tank; 8-a waste liquid tank; 9a-KI diluent pump; 9b-KCl electrode immersion liquid pump; 10-a waste liquid pump; 11-a liquid pump of the material to be detected; 12-a liquid storage tank, a conveying pipeline or a tower to be tested; 13-liquid level meter.
Detailed Description
The structure, principle and operation of the apparatus according to the present invention will be described in further detail with reference to the accompanying drawings.
The application provides a concentration analysis equipment and method of iodine-containing hydriodic acid, when determining the concentration of iodine-containing hydriodic acid, 3 independent variables closely related to the solution concentration including temperature are determined, and standard commercial devices are adopted when determining the variables, so that the accuracy of determination is ensured. Specifically, the temperature sensor is used to measure the temperature value of iodine-containing hydriodic acid solution, the hydrogen ion indicating electrode and the oxidation-reduction potential electrode are used to measure two voltage (potential) values of the solution, and the concentration of the feed liquid is rapidly calculated under the assistance of a computer. Under the current technical conditions and market supply conditions, the temperature sensor, the hydrogen ion indicating electrode and the oxidation-reduction potential electrode are all conventional devices, and the repeatability and the accuracy of a measuring result can be ensured.
As shown in fig. 1, the concentration analysis equipment for iodine-containing hydroiodic acid provided by the invention comprises a computer 1, a hydrogen ion indicating electrode 2, an oxidation-reduction potential electrode 3, a temperature sensor 4, a potentiometer 5, a measuring cell 6, a KI diluent storage tank 7a, a KCl electrode soaking solution storage tank 7b, a waste liquid tank 8 and a pump; the pump comprises a liquid pump 11 of the material to be measured, a KI diluent pump 9a, a KCl electrode soaking liquid pump 9b and a waste liquid pump 10; the measuring pool 6 is connected with a material liquid storage tank 12 to be measured and a conveying pipeline or a tower 12 through a material liquid pump 11 to be measured and a pipeline; the KI diluent storage tank 7a is connected with the measuring tank 6 through a KI diluent pump 9a and a pipeline; the KCl electrode soak solution storage tank 7b is connected with the measuring tank 6 through a KCl electrode soak solution pump 9b and a pipeline; the measuring tank 6 is connected with a waste liquid tank 8 through a pipeline and a waste liquid pump 10; a hydrogen ion indicating electrode 2, an oxidation-reduction potential electrode 3 and a temperature sensor 4 are arranged in the measuring cell 6, and the hydrogen ion indicating electrode 2 and the oxidation-reduction potential electrode 3 are connected with the potentiometer 5 through leads; the potentiometer 5 and the temperature sensor 4 are respectively connected with the computer 1 through signal wires.
The temperature sensor 4 of the present invention may be an independent sensor, and may also be placed in the hydrogen ion indicating electrode 2 or the oxidation-reduction potential electrode 3, that is, the hydrogen ion indicating electrode 2 or the oxidation-reduction potential electrode 3 may have a built-in temperature sensor.
In order to enable the temperature measurement value to be closer to the actual situation, the measurement pool 6, the KI diluent storage tank 7a, the material liquid pump 11 to be measured, the KI diluent liquid pump 9a, the KCl electrode soaking liquid pump 9b, the waste liquid pump 10 and the pipeline connecting the pumps are provided with temperature control and insulation facilities. The liquid pump 11 of the material to be measured, the KI diluent pump 9a, the KCl electrode soaking liquid pump 9b and the waste liquid pump 10 are connected with the computer 1 through control lines, so that the computer can remotely control the pumps; the measuring cell 6 can also be equipped with a level indicator 13, which is connected to a computer via a control line and can be monitored remotely by the computer.
The invention provides a method for analyzing the concentration of iodine-containing hydriodic acid, which specifically comprises the following steps:
1) before testing, firstly, starting a waste liquid pump 10 to empty a measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
2) starting a liquid pump 11 of the material to be measured, conveying 0.1-500 mL iodine-containing hydroiodic acid to be measured into the measuring pool 6) from a storage tank, a conveying pipeline or a tower 12 containing the material to be measured, closing the liquid pump 11 of the material to be measured, and stopping a material flow pipeline between the storage tank 12, the conveying pipeline or the tower 12 of the material to be measured and the measuring pool 6;
3) starting a KI dilution pump 9a, inputting KI diluent into the measuring tank 6 from a KI diluent storage tank 7a, closing the KI dilution pump 9, and stopping a material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6; the concentration of KI diluent is 0.1-3 mol/L, and the delivery volume is 0.1-1000 mL; when the HI concentration in the iodine-containing hydroiodic acid to be detected is known to be lower than 1mol/L, and I2When the concentration is lower than 0.5mol/L, KI diluent can not be input, namely: the iodine-containing hydriodic acid feed liquid conveyed to the measuring pool is directly subjected to subsequent temperature and potential measurement without being diluted by KI diluent;
4) the hydrogen ion indicating electrode 2 and the oxidation-reduction potential electrode 3 measure two groups of potential values of the solution in the measuring tank 6 through a potentiometer 5, the temperature sensor 4 measures the temperature value of the solution in the measuring tank 6, the potential values and the temperature values are transmitted to the computer 1, and the computer 1 calculates the concentration of the discharged liquid by utilizing the stored calculation softwareAnd displaying; the mathematical model on which the software mainly depends is the concentration c of HI in iodine-containing hydriodic acid feed liquidHI、I2Concentration c ofI2The temperature t of the feed liquid, the measured potential values of the hydrogen ion indicating electrode and the oxidation-reduction potential electrode (u respectively)1And u2) The relational expression of (1):
u1＝f1(t,cHI,cI2)
u2＝f2(t,cHI,cI2)
the two equations are combined, i.e. t and u can be measured1And u2Calculating the concentration data c of the mixed solution in the measuring cellHIAnd cHI(ii) a The concentration data of the original iodine-containing hydriodic acid feed liquid to be detected can be calculated reversely according to the volume ratio of the KI diluent to the original iodine-containing hydriodic acid feed liquid to be detected;
5) after the determination is finished, emptying the measuring tank, starting a waste liquid pump 10 to empty the measuring tank 6 at the moment, enabling the discharged materials to flow into a waste liquid tank 8, then closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
6) after the measuring cell is emptied, in order to ensure the accuracy of subsequent measurements, the measuring cell is cleaned once, namely: starting a KI dilution pump 9a, inputting KI diluent into the measuring tank 6 from a KI diluent storage tank 7a, closing the KI dilution pump 9a, and stopping a material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6; the delivery volume of KI diluent is 5-1000 mL; starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
7) after the cleaning is finished, the electrode soaking solution (balancing solution) is filled into the measuring cell to ensure that the electrode is in a good state and is ready for the next measurement. The specific operation is as follows: and opening a KCl electrode soak solution pump 9b to input the KCl electrode soak solution from a KCl electrode soak solution storage tank 7b to the measuring tank 6, closing the KCl electrode soak solution pump 9b, stopping a material flow pipeline between the KCl electrode soak solution storage tank 7b and the measuring tank 6, and controlling the concentration of the KCl electrode soak solution to be 0.1-4 mol/L.
The measured feed liquid of the invention is from the iodine-containing hydriodic acid storage tank, pipeline or the inside of the rectifying tower.
Example 1
According to the attached figure 1 and the principle thereof, a concentration measuring device is assembled for an iodine-containing hydriodic acid storage tank 12 with the volume of 20L, a temperature sensor 4 is a K-type thermocouple G703595 manufactured by WATLOW company, a hydrogen ion indicating electrode 2 is an 6.0262.100-type pH electrode manufactured by Switzerland Wantong company, and an oxidation-reduction potential electrode 3 is a PT TITRODE WOC-type composite platinum electrode manufactured by Switzerland Wantong company. The effective volume of the measuring cell 6 is 100 mL. The concentration of KI diluent is 2mol/L, and the concentration of KCl electrode soak solution is 3 mol/L. In FIG. 1, the pumps corresponding to the KI diluent pump 9a and the feed liquid pump 11 to be measured are QG150-Q1CKC type metering pumps of American FMI company with back pressure valves. In FIG. 1, the KCI electrode immersion liquid pump 9b and the waste liquid pump 10 correspond to a Proming GAL type diaphragm pump with a back pressure valve. The start and stop of the pumps are remotely controlled by a computer.
The concentration of the feed liquid is measured by the following steps:
1) before testing, firstly, a waste liquid pump 10 is started to empty the measuring tank 6, the discharged materials flow into a waste liquid tank 10, the waste liquid tank 10 is closed, and a material flow pipeline between the measuring tank 6 and the waste liquid tank 8 is cut off;
2) starting a liquid pump 11 of the material to be measured, conveying 5mL of iodine-containing hydriodic acid to be measured into the measuring tank 6 from a liquid storage tank 12 of the material to be measured, closing the liquid pump 11 of the material to be measured, and stopping a material flow pipeline between the liquid storage tank 12 of the material to be measured and the measuring tank 6;
3) starting a KI diluent pump 9a, inputting 45mL of KI diluent into the measuring tank 6 from a KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping a material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6;
4) the hydrogen ion indicating electrode 2 and the oxidation-reduction potential electrode 3 measure two groups of potential values of the solution in the measuring pool 6 through the potentiometer 5, the temperature sensor 4 measures the temperature value of the solution in the measuring pool 6, the potential values and the temperature value are transmitted to the computer, and the computer 1 calculates and displays the concentration of the discharged liquid by utilizing the stored calculation software.
5) After the end of the assay, the measurement cell was emptied, at which time: starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank (8), closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
6) after the measuring cell is emptied, in order to ensure the accuracy of subsequent measurements, the measuring cell is cleaned once, namely: and (3) starting the KI diluent pump 9a, inputting 100mL of KI diluent into the measuring tank 6 from the KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping the material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6. Starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
7) after the cleaning is finished, the electrode soaking solution (balancing solution) is filled into the measuring cell to ensure that the electrode is in a good state and is ready for the next measurement. The specific operation is as follows: and (3) starting a KCl electrode soak solution pump, inputting 60mL of KCl electrode soak solution into the measurement pool 6 from the KCl electrode soak solution storage tank 7b, closing the KCl electrode soak solution pump, and stopping a material flow pipeline between the KCl electrode soak solution storage tank 7b and the measurement pool 6.
The sample liquid storage tank 12 or the tower to be measured is respectively used for storing 1#, 2# and 3# iodine-containing hydriodic acid samples to be measured, concentration measurement is carried out by adopting the equipment and the method, the measurement results are listed in the following table, and the table also lists the concentrations of the 1#, 2# and 3# samples obtained by adopting a conventional titration method for comparison.
Example 2:
according to the attached figure 1 and the principle thereof, a concentration measuring device is arranged on a conveying pipeline containing iodine hydriodic acid, namely a liquid pump 11 of a material to be measured and a pipeline thereof are used for sampling from the pipeline.
The hydrogen ion indicating electrode 2 is an i-Ecotrode plus type pH electrode of Switzerland Vanton, and the oxidation-reduction potential electrode 3 is a PT TITRODE WOC type composite platinum electrode of Switzerland Vanton. Because the i-Ecotrode plus type pH electrode integrates a temperature detection function, the device is not additionally provided with a separate temperature sensor.
The effective volume of the measuring cell 6 is 300 mL. The concentration of KI diluent is 3mol/L, and the concentration of KCl electrode soak solution is 3 mol/L. The pumps corresponding to the KI diluent 9a and the feed liquid pump 11 to be measured in the attached drawing 1 are QG150-Q1CKC type metering pumps of American FMI company with a back pressure valve. In fig. 1, the feed pump 11 to be measured and the waste liquid pump 10 correspond to each other and are a purominate GAL type diaphragm pump having a back pressure valve. The start and stop of the pumps are remotely controlled by a computer.
The measuring cell 6 is equipped with a liquid level meter 13, which can be monitored by a computer to ensure that the hydrogen ion indicator electrode 2 and the oxidation-reduction potential electrode 3 are effectively immersed by the liquid at the time of measurement.
The concentration of the feed liquid is measured by the following steps:
1) before testing, firstly, starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6) and the waste liquid tank 8;
2) starting a liquid pump 11 of the material to be measured, conveying 10mL of iodine-containing hydroiodic acid to be measured into the measuring pool 6 through a pipeline where the iodine-containing hydroiodic acid is located, closing the liquid pump 11 of the material to be measured, and stopping a material flow pipeline between a pipe 12 of the material to be measured and the measuring pool 6;
3) starting a KI diluent pump 9a, inputting 90mL of KI diluent into the measuring tank 6 from a KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping a material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6;
4) the hydrogen ion indicating electrode 2 and the oxidation-reduction potential electrode 3) measure two groups of potential values of the solution in the measuring cell 6 through a potentiometer 5), the potential values and a temperature value measured by a temperature sensor integrated in the hydrogen ion indicating electrode 2 are transmitted to a computer, and the computer 1 calculates and displays the concentration of the discharged liquid by utilizing computing software stored in the computer.
5) After the end of the assay, the measurement cell was emptied, at which time: starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
6) after the measuring cell is emptied, in order to ensure the accuracy of subsequent measurements, the measuring cell is cleaned once, namely: and (3) starting the KI diluent pump 9a, inputting 300mL of KI diluent into the measuring tank 6 from the KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping the material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6. Starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
7) after the cleaning is finished, the electrode soaking solution (balancing solution) is filled into the measuring cell to ensure that the electrode is in a good state and is ready for the next measurement. The specific operation is as follows: and (3) starting a KCl electrode soak solution pump to input 200mL of KCl electrode soak solution from a KCl electrode soak solution storage tank 7b to the measurement tank 6, closing the KCl electrode soak solution pump, and stopping a material flow pipeline between the KCl electrode soak solution storage tank 7b and the measurement tank 6.
When 4# and 5# iodine-containing hydriodic acid samples were fed into the pipeline, concentration measurements were made using the above-described apparatus and method, and the results are shown in the following table, which shows, for comparison, the concentrations of samples # 4 and # 5 obtained by the conventional titration method.
Example 3:
the concentration analysis device in example 2 is arranged at the bottom of the iodine-containing hydriodic acid rectification tower, i.e. the feed liquid pump 11 to be tested and the pipeline thereof are used for sampling from the bottom of the rectification tower. The concentration of the feed liquid is measured by the following steps:
1) before testing, firstly, starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
2) starting a liquid pump 11 of the material to be measured, conveying 60mL of iodine-containing hydroiodic acid to be measured into the measuring pool 6 from the HIx rectifying tower kettle in which the iodine-containing hydroiodic acid is positioned, closing the liquid pump 11 of the material to be measured, and stopping a material flow pipeline between a material liquid conveying pipeline 12 of the material to be measured and the measuring pool 6;
3) starting a KI diluent pump 9a, inputting 90mL of KI diluent into the measuring tank 6 from a KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping a material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6;
4) the hydrogen ion indicating electrode 2 and the oxidation-reduction potential electrode 3 measure two groups of potential values of the solution in the measuring pool 6 through a potentiometer 5, the potential values and a temperature value measured by a temperature detecting device integrated in the hydrogen ion indicating electrode 2 are transmitted to the computer 1, and the computer calculates and displays the concentration of the discharged liquid by utilizing the stored calculation software.
5) After the end of the assay, the measurement cell was emptied, at which time: starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
6) after the measuring cell is emptied, in order to ensure the accuracy of subsequent measurements, the measuring cell is cleaned once, namely: and (3) starting the KI diluent pump 9a, inputting 80mL of KI diluent into the measuring tank 6 from the KI diluent storage tank 7a, closing the KI diluent pump 9a, and stopping the material flow pipeline between the KI diluent storage tank 7a and the measuring tank 6. Starting a waste liquid pump 10 to empty the measuring tank 6, enabling the discharged materials to flow into a waste liquid tank 8, closing the waste liquid pump 10, and stopping a material flow pipeline between the measuring tank 6 and the waste liquid tank 8;
7) after the cleaning is finished, the electrode soaking solution (balancing solution) is filled into the measuring cell to ensure that the electrode is in a good state and is ready for the next measurement. The specific operation is as follows: and (3) starting a KCl electrode soak solution pump to input 60mL of KCl electrode soak solution into the measurement pool 6 from the KCl electrode soak solution storage tank 7b, and closing the KCl electrode soak solution pump to stop a material flow pipeline between the KCl electrode soak solution storage tank 7b) and the measurement pool 6.
When 6# and 7# iodine-containing hydriodic acid samples were fed into the pipeline, concentration measurements were made using the above-described apparatus and method, and the results are shown in the following table, which shows, for comparison, the concentrations of the samples # 6 and # 7 obtained by the conventional titration method.
Claims (6)
1. The utility model provides an iodine-containing hydriodic acid's concentration analytical equipment which characterized in that: the equipment comprises a computer (1), a hydrogen ion indicating electrode (2), an oxidation-reduction potential electrode (3), a temperature sensor (4), a potentiometer (5), a measuring pool (6), a KI diluent storage tank (7a), a KCl electrode soak storage tank (7b), a waste liquid tank (8) and a pump; the pump comprises a liquid pump (11) of the material to be measured, a KI diluent pump (9a), a KCl electrode soaking liquid pump (9b) and a waste liquid pump (10); the measuring pool (6) is connected with a material liquid storage tank (12) to be measured and a conveying pipeline or a tower through a material liquid pump (11) to be measured and a pipeline; the KI diluent storage tank (7a) is connected with the measuring tank (6) through a KI diluent pump (9a) and a pipeline; the KCl electrode soak solution storage tank (7b) is connected with the measuring tank (6) through a KCl electrode soak solution pump (9b) and a pipeline; the measuring tank (6) is connected with a waste liquid tank (8) through a pipeline and a waste liquid pump (10); a hydrogen ion indicating electrode (2), an oxidation-reduction potential electrode (3) and a temperature sensor (4) are arranged in the measuring cell (6), and the hydrogen ion indicating electrode (2) and the oxidation-reduction potential electrode (3) are connected with the potentiometer (5) through leads; the potentiometer (5) and the temperature sensor (4) are respectively connected with the computer (1) through signal wires.
2. An iodine-containing hydriodic acid concentration analysis apparatus according to claim 1, wherein: the temperature sensor (4) is arranged independently, or is arranged in the hydrogen ion indicating electrode (2), or is arranged in the oxidation-reduction potential electrode (3).
3. An iodine-containing hydriodic acid concentration analysis apparatus according to claim 1, wherein: the measuring tank (6), the KI diluent storage tank (7a), the material liquid pump (11) to be measured, the KI diluent liquid pump (9a), the KCl electrode soaking liquid pump (9b), the waste liquid pump (10) and the pipeline of the connecting pump are provided with temperature control and insulation facilities.
4. An iodine-containing hydriodic acid concentration analysis apparatus according to claim 1, 2 or 3, wherein: the device is characterized in that the liquid pump (11) of the material to be measured, the KI diluent pump (9a), the KCl electrode soaking liquid pump (9b) and the waste liquid pump (10) are connected with the computer (1) through control lines.
5. The iodine-containing hydriodic acid concentration analysis apparatus according to claim 4, wherein: and a liquid level meter (13) is arranged in the measuring pool (6) and is connected with the computer (1) through a control circuit.
6. A method for analyzing the concentration of iodine-containing hydriodic acid using the apparatus of claim 1, comprising the steps of:
1) starting a waste liquid pump (10), emptying the measuring tank (6), enabling the discharge to flow into a waste liquid tank (8), and then closing the waste liquid pump (10) to stop a material flow pipeline between the measuring tank (6) and the waste liquid tank (8);
2) starting a liquid pump (11) of the material to be measured, conveying 0.1-500 mL of iodine-containing hydriodic acid material liquid to be measured into a measuring pool (6) through a material liquid pipeline to be measured, and then closing the liquid pump (11) of the material to be measured to stop a material liquid storage tank, a conveying pipeline or a material flow pipeline between a tower and the measuring pool (6);
3) starting a KI diluent pump (9a), inputting KI diluent into the measuring tank (6) from a KI diluent storage tank (7a), and then closing the KI diluent pump (9a) to stop a material flow pipeline between the KI diluent storage tank (7a) and the measuring tank (6); the concentration of the KI diluent is 0.1-3 mol/L, and the delivery volume is 0.1-1000 mL;
4) the potentiometer (5) respectively measures two groups of potential values u of the solution in the measuring cell (6) through the hydrogen ion indicating electrode (2) and the oxidation-reduction potential electrode (3)1And u2The temperature sensor (4) measures the temperature value t of the solution in the measuring cell (6) and two groups of potential values u1And u2And the temperature value t is transmitted to a computer, and the computer (1) calculates the concentration of the discharged liquid by utilizing the stored calculation software and displays the concentration;
the calculation software performs calculation according to the following equation set:
u1＝f1(t,cHI,cI2)
u2＝f2(t,cHI,cI2)
equation f1(t,cHI,cI2) Is t, cHIAnd cI2Three variable pairs u1Mathematical expression of (a), (b), f)2(t,cHI,cI2) Is t, cHIAnd cI2Three variable pairs u2A mathematical expression of (a), wherein cHIIs the concentration of HI in the iodine-containing hydriodic acid feed liquid, cI2Is I2T is the temperature value of the solution in the measuring cell;
combining the above two equations, and determining t and u1And u2Namely, the concentration data c of the solution in the measuring cell is calculatedHIAnd cHI(ii) a Then, inversely calculating the concentration data of the original iodine-containing hydriodic acid feed liquid to be detected according to the volume ratio of the KI diluent to the original iodine-containing hydriodic acid feed liquid to be detected;
5) starting a waste liquid pump (10) to empty the material liquid in the measuring tank (6), sending the discharged material liquid to a waste liquid tank (8), and then closing the waste liquid pump (10) to stop a material flow pipeline between the measuring tank (6) and the waste liquid tank (8);
6) starting a KI diluent pump (9a), inputting KI diluent into the measuring tank (6) from a KI diluent storage tank (7a), and closing the KI diluent pump (9a) to stop a material flow pipeline between the KI diluent storage tank (7a) and the measuring tank (6); the delivery volume of KI diluent is 5-1000 mL; starting a waste liquid pump (10) to empty the measuring tank (6), sending the discharged liquid to a waste liquid tank (8), then closing the waste liquid pump (10), and stopping a material flow pipeline between the measuring tank (6) and the waste liquid tank (8);
7) and (3) starting a KCl electrode soaking liquid pump (9b), inputting the KCl electrode soaking liquid into the measuring pool (6) from a KCl electrode soaking liquid storage tank (7b), closing the KCl electrode soaking liquid pump (9b), stopping a material flow pipeline between the KCl electrode soaking liquid storage tank (7b) and the measuring pool (6), and controlling the concentration of the KCl electrode soaking liquid to be 0.1-4 mol/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005077145A (en) * | 2003-08-28 | 2005-03-24 | Japan Atom Energy Res Inst | Quantitative analytical method for (iodine + hydroiodic acid + sulfuric acid) solution |
| KR20100078182A (en) * | 2008-12-30 | 2010-07-08 | 한국에너지기술연구원 | The method of quantitative analysis for h2so4-hi-h2o-i2 system solution in high concentration condition of i2 without calibration |
| CN103048219A (en) * | 2012-12-05 | 2013-04-17 | 清华大学 | Analytical method of iodine-containing hydriodic acid concentration |
| CN103048220A (en) * | 2012-12-05 | 2013-04-17 | 清华大学 | Iodine hydroiodic acid container capable of displaying liquid concentration on line |
| CN105675809A (en) * | 2016-01-15 | 2016-06-15 | 清华大学 | Analysis method of concentration of HI-I2-H2O ternary solution |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005077145A (en) * | 2003-08-28 | 2005-03-24 | Japan Atom Energy Res Inst | Quantitative analytical method for (iodine + hydroiodic acid + sulfuric acid) solution |
| KR20100078182A (en) * | 2008-12-30 | 2010-07-08 | 한국에너지기술연구원 | The method of quantitative analysis for h2so4-hi-h2o-i2 system solution in high concentration condition of i2 without calibration |
| CN103048219A (en) * | 2012-12-05 | 2013-04-17 | 清华大学 | Analytical method of iodine-containing hydriodic acid concentration |
| CN103048220A (en) * | 2012-12-05 | 2013-04-17 | 清华大学 | Iodine hydroiodic acid container capable of displaying liquid concentration on line |
| CN105675809A (en) * | 2016-01-15 | 2016-06-15 | 清华大学 | Analysis method of concentration of HI-I2-H2O ternary solution |
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