Online characterization processes of free chlorine and device in a kind of hydrogen chloride building-up process
Technical field
The present invention relates to online characterization processes of free chlorine and device in a kind of hydrogen chloride building-up process.
Background technology
In poly production run, one of common security incident is because of free chlorine that contains in the hydrogen chloride gas and acetylene gas generation vigorous reaction, generate chloroacetylene, and the chloroacetylene instability that generates, be easy to decompose, finally generate hydrogen chloride and carbon, in course of reaction, discharge a large amount of heats, cause explosive combustion, the part of damaging mixed dehydration sets pipeline.This type of accident causes very big threat owing to easily send out, take place frequently to the safety in production and the stable operation of installing.Particularly many enterprises reduce the excess hydrogen value for the high hydrogen chloride gas of production purity, and this must increase the probability of producing free chlorine, have caused the generation probability of accident.
At present in the industry there be the method for common detection excess chlorine: 1. acetylene autovalve and mixer outlet temperature, temperature changing speed are chain, and when temperature or rate temperature change surpassed certain numerical value, the acetylene autovalve was closed immediately, simultaneously warning.2. by control devices such as orifice flowmeter metering and automatic mixings, the flow of control chlorine and hydrogen guarantees that the purity of hydrogen chloride is stable.3. a little combination gas is set on hydrogen chloride dispense station outlet header, when chlorine is excessive, finds early and take measures.4. the purity of instrumental analysis hydrogen chloride is reproduced the content that detects free chlorine.5. the hydrogen chloride dechlorination jar of dress activated charcoal in adopting, the free chlorine in the absorption hydrogen chloride.6. visor is observed the color of flame, control valve, the purity of assurance hydrogen chloride.7. adopt the hydrochloric acid stripping to take off suction, avoid the free chlorine in the hydrogen chloride, improve the purity of hydrogen chloride simultaneously.But above method labour intensity is big, and equipment is many.
Delivered at 2006 the 7th phases " Polyvinylchloride " magazine and to have proposed the micro-chlorine early warning measure of crossing in the article that is entitled as " early detection that hydrogen chloride is crossed chlorine in the mixed gas ", its measure is to set a warning reference value, converter circulating hot water temperature and heater outlet temperature have a difference A, when the A value less than the warning reference value time, system carried out the chlorine early warning at once, prompting operation people and hydrogen chloride synthetic furnace post are got in touch, make it to adopt an effective measure rapidly, emergency treatment, pay close attention to working conditions change simultaneously, get in touch with the acetylene post in case of necessity, prepare at any time to stop in emergency, avoid emergency operation that system pressure is impacted.
Delivered at " Polyvinylchloride " magazine of 2004 the 4th phases be entitled as " application of small-sized DCS synthetic control system of hydrogen chloride in PVC produces " literary composition narrated Shenyang Chemical Co., Ltd. adopt the small-sized DCS control system PROCIDIA of Siemens Mu Er company PVC is produced in the control of synthesising hydrogen production run, having introduced controlling schemes, the formation of control system, control station ICONFIG is connected with active station WINCC's, after this kind control system puts into operation, improved production automation degree, improve labour productivity, reduced working strength of workers.The hydrogen chloride volume fraction has improved 2%, loses and save hydrogen usage calculating according to reducing tail gas emptying VCM, but the about 400,000 yuan/a of cost saving.
Summary of the invention
The purpose of this invention is to provide online characterization processes of free chlorine and device in a kind of hydrogen chloride building-up process.
The invention provides the online characterization processes of free chlorine in a kind of hydrogen chloride building-up process, the hydrogen chloride gas that wherein contains chlorine enters in the pick-up unit by access to plant, chlorine in the hydrogen chloride gas makes the electrode in the pick-up unit produce potential difference (PD), potential difference (PD) information is through being delivered to the collecting and distributing control center of DCS, control center can control hydrogen valve enlargement discharge and control chlorine valve minimizing flow simultaneously, thereby reaches the purpose of eliminating free chlorine.
And enter in the hydrogen chloride gas in the pick-up unit chlorine also with described pick-up unit in indicator generation metachromasia.
The present invention also provides a kind of device of finishing the online characterization processes of free chlorine in the hydrogen chloride building-up process, pick-up unit wherein comprises the container of depositing electrolytic solution at least, the electrode, electrolytic solution, the described container that are provided with in the container in order to the indicating potential difference are provided with sewage draining exit, and described electrode is connected to the collecting and distributing control center of DCS outside the sensing chamber.
Pick-up unit also comprises the container of depositing indicator, in indicator is housed, the described container of depositing electrolytic solution connects together by pipeline with the described container of depositing indicator.
Contain the device of free chlorine in online detection provided by the invention and the control hydrogen chloride gas, wherein the electrolytic solution in depositing the container of electrolytic solution contains indicator.
Access to plant comprises pin hole valve and sampler.
Indicator is a kind of in starch-kalium iodide solution or the o-tolidine solution.
Electrode is made up of contrast electrode and indicator electrode.
Contrast electrode is a saturated calomel electrode.
Electrolytic solution is hydrochloric acid.
Adopt the technology of the online detection of free chlorine of the present invention; Require chlorine, hydrogen proportioning excess hydrogen all the time; Require compositor to mix, burn thoroughly; And when hydrogen chloride gas is carried out online detection, correct immediately, do not allow free chlorine to the purpose of subsequent processing to ensure safety in production in case chlorine is excessive.
Adopt the device of the online detection of free chlorine of the present invention.The free chlorine pick-up unit (seeing figure one and two for details) of equipment on hydrogen chloride gas synthetic furnace exit or synthetic furnace and refrigeratory connecting pipe, its principle is: the hydrogen chloride gas of drawing from sample tap enters the pick-up unit, electrolytic solution and electrode are housed, when the accurate current potential of hydrogen chloride gas in pick-up unit.When containing micro-chlorine in the hydrogen chloride gas, the hydrogen chloride gas of equal volume dissolves in electrolytic solution, this moment, pH and the above-mentioned pH in the electrolytic solution was inequality, the potential difference (PD) that produce this moment between indicator electrode and contrast electrode is different from reference potential, this current potential difference different with reference potential reaches the collecting and distributing control center of DCS, automatically regulate hydrogen valve or chlorine valve and eliminate free chlorine, pick-up unit of the present invention is controlled highly sensitive, to guarantee the safety in production of postorder operation.
Description of drawings
Fig. 1 is the device as the online detection of free chlorine in embodiment 1, the example 3 described hydrogen chloride building-up processes.
Fig. 2 is the device as the online detection of free chlorine in the embodiment 2 described hydrogen chloride building-up processes.
Embodiment
Embodiment 1
The technology and the device of the online detection of free chlorine in the hydrogen chloride building-up process of employing Fig. 1, chlorine and hydrogen is fully burning in hydrogen chloride synthetic furnace 11.Generate hydrogen chloride gas, in order to guarantee to allow the complete fuel of chlorine, usually allow hydrogen excessive 2 ~ 5%, this gas enters sampler 13 along pipeline 12, open needle valve 14, a certain amount of hydrogen chloride gas that carries chlorine enters in the container 15 of depositing electrolytic solution, the electrolysis of hydrochloric acid liquid that contains its volume 2/3rds in the container of this moment, the mass concentration of electrolysis of hydrochloric acid liquid is 20~34%, electrode 16 and 17 in the electrolytic solution, (electrode 16 is a contrast electrode) links to each other with power supply, and 16 and 17 also are connected the collecting and distributing control center of DCS, when not containing the chlorine of end burning in the hydrogen chloride gas, identical with the reference voltage that is provided with in the collecting and distributing control center of DCS from 16 with the voltage of 17 outputs, when containing the chlorine of end burning in the hydrogen chloride, when the voltages of 16 and 17 outputs surpassed the reference voltage that the collecting and distributing control center of DCS is provided with, the collecting and distributing control center of DCS sounded the alarm.
Do not enter the hydrogen chloride gas of depositing electrolyte container, enter in the condenser 18, next procedure is delivered in its cooling along pipeline 12 along sample tap.On pipeline 12, also be provided with manograph 19 and thermal detector 20 to measure the pressure and temperature of hydrogen chloride gas.
And in depositing electrolyte container, contain from the indicator inlet 21 starch potassium iodide indicator that splash into, its mass concentration is 0.5%~15%, there is the chlorine of trace to enter when depositing electrolyte container 15, starch potassium iodide indicator generation redox reaction in chlorine and the electrolytic solution wherein, make indicator become blue, simultaneously whole electrolytic solution becomes blue.
In the operating process of next time, the electrolytic solution of variable color is discharged from sewage draining exit 23, with pure water washing electrode 16,17 and deposit electrolyte container 15, again by entering the mouth 24 to wherein adding the electrolytic solution that configures, and by indicator inlet 21 to wherein adding indicator to be used for operation next time.
Embodiment 2
The technology and the device of the online detection of free chlorine in the hydrogen chloride building-up process of employing Fig. 2, unreacted chlorine and hydrogen enter sampler 23 along pipeline 22, open needle valve 24, the hydrogen chloride gas that carries chlorine and hydrogen of trace enters the container 25 of depositing electrolytic solution, wherein contain the electrolysis of hydrochloric acid liquid that is higher than pipeline 21 this moment, the mass concentration of electrolysis of hydrochloric acid liquid is 20~34%, electrode 26 and 27 in the electrolytic solution, (26 is contrast electrode) links to each other with power supply, and 26 and 27 also are connected the collecting and distributing control center of DCS, when the voltages of 26 and 27 outputs surpassed the reference voltage that the collecting and distributing control center of DCS is provided with, DCS control center sounded the alarm.
The hydrogen chloride gas that a part is not dissolved in the electrolysis of hydrochloric acid liquid enters in the container 32 of depositing indicator along pipeline 31, o-tolidine solution indicator wherein is housed, its mass concentration is 0.5%~15%, when carrying free chlorine in the hydrogen chloride gas, o-tolidine solution indicator discoloration.
Do not enter the hydrogen chloride gas of indicator jar, enter in the condenser 28, next procedure is delivered in its cooling along pipeline 22 along sample tap.On pipeline 22, also be provided with manograph 29 and thermal detector 30 to measure the pressure and temperature of hydrogen chloride gas.
In the operating process of next time, with the electrolytic solution of variable color from pipeline 31 enters sensing chamber 25, with pure water washing electrode 26,27 and the container 32 of depositing indicator, and by sewage draining exit 33 effluent discharges, in the container of depositing indicator, add indicator to be used for operation next time again by 34 electrolytic solution that interpolation configures in sensing chamber that enter the mouth, and by indicator jar inlet 35.
Embodiment 3
The technology and the device of the online detection of free chlorine in the hydrogen chloride building-up process of employing Fig. 1, chlorine and hydrogen is fully burning in hydrogen chloride synthetic furnace 11.Generate hydrogen chloride gas, in order to guarantee to allow the complete fuel of chlorine, usually allow hydrogen excessive 2 ~ 5%, this gas enters sampler 13 along pipeline 12, open needle valve 14, a certain amount of hydrogen chloride gas that carries hydrogen enters in the container 15 of depositing electrolytic solution, the electrolysis of hydrochloric acid liquid that contains its volume 2/3rds in the container of this moment, the mass concentration of electrolysis of hydrochloric acid liquid is 20~34%, electrode 16 and 17 in the electrolytic solution, (electrode 16 is a contrast electrode) links to each other with power supply, and 16 and 17 also are connected the collecting and distributing control center of DCS, when not containing the chlorine of end burning in the hydrogen chloride, identical with the reference voltage that is provided with in the collecting and distributing control center of DCS from 16 with the voltage of 17 outputs, when containing the chlorine of end burning in the hydrogen chloride, when the voltages of 16 and 17 outputs surpassed the reference voltage that the collecting and distributing control center of DCS is provided with, the collecting and distributing control center of DCS sounded the alarm.
Do not enter the hydrogen chloride gas of depositing electrolyte container, enter in the condenser 18, next procedure is delivered in its cooling along pipeline 12 along sample tap.On pipeline 12, also be provided with manograph 19 and thermal detector 20 to measure the pressure and temperature of hydrogen chloride gas.In, next procedure is delivered in its cooling.On pipeline 12, also be provided with manograph 19 and thermal detector 20 to measure the pressure and temperature of hydrogen chloride gas.
In the operating process of next time, electrolytic solution is discharged from sewage draining exit 23, with pure water washing electrode 16,17 and deposit electrolyte container 15, again by entering the mouth 24 to wherein adding the electrolytic solution that configures, and by indicator inlet 21 to wherein adding indicator to be used for operation next time.