CN112213439A - Device and method for measuring content of dissolved hydrogen in high-temperature high-pressure steam - Google Patents
Device and method for measuring content of dissolved hydrogen in high-temperature high-pressure steam Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000001301 oxygen Substances 0.000 claims abstract description 126
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 110
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 69
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 35
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 35
- 239000010935 stainless steel Substances 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 33
- 238000005070 sampling Methods 0.000 claims abstract description 32
- 238000005259 measurement Methods 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 6
- 231100000572 poisoning Toxicity 0.000 claims description 6
- 230000000607 poisoning effect Effects 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002926 oxygen Chemical class 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 239000000072 sodium resin Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 3
- 229920005372 Plexiglas® Polymers 0.000 claims 3
- 238000000605 extraction Methods 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 20
- 229910052708 sodium Inorganic materials 0.000 abstract description 20
- 239000011734 sodium Substances 0.000 abstract description 20
- 238000012544 monitoring process Methods 0.000 abstract description 7
- 238000002347 injection Methods 0.000 description 27
- 239000007924 injection Substances 0.000 description 27
- 238000011033 desalting Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
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- 239000003814 drug Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 3
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- 230000003287 optical effect Effects 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
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- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
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- 230000036632 reaction speed Effects 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
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Abstract
本发明涉及溶解氢含量测量装置和方法，它属于监测领域。本发明包括取样和流量控制单元、钠型树脂柱、不锈钢三通、注射泵、除盐水箱、溶解氧表流通池、钯催化树脂柱、溶解氧表和可编程序控制器，取样和流量控制单元包括取样管道、针阀和流量计，钠型树脂柱与取样和流量控制单元相连，溶解氧表流通池包括溶解氧表流通池一和溶解氧表流通池二，不锈钢三通一端与钠型树脂柱相连，另外两端分别与溶解氧表流通池一及注射泵出口相连，注射泵另一端与除盐水箱相连，溶解氧表与溶解氧表流通池相连，注射泵与可编程序控制器相连。本发明同时测量水样中溶解氧和溶解氢含量，溶解氧表测量准确就保证溶解氢测量结果的准确性，且测量结果不受溶解氧的影响。
The invention relates to a dissolved hydrogen content measuring device and method, which belong to the field of monitoring. The present invention includes sampling and flow control unit, sodium type resin column, stainless steel tee, syringe pump, demineralized water tank, dissolved oxygen meter flow cell, palladium catalytic resin column, dissolved oxygen meter and programmable controller, sampling and flow control The unit includes a sampling pipeline, a needle valve and a flow meter. The sodium-type resin column is connected to the sampling and flow control unit. The dissolved oxygen meter flow cell includes dissolved oxygen meter flow cell one and dissolved oxygen meter flow cell two. One end of the stainless steel tee is connected to the sodium type. The resin column is connected, the other two ends are connected to the dissolved oxygen meter flow cell 1 and the outlet of the syringe pump, the other end of the syringe pump is connected to the demineralized water tank, the dissolved oxygen meter is connected to the dissolved oxygen meter flow cell, and the syringe pump is connected to the programmable controller. connected. The invention simultaneously measures the dissolved oxygen and dissolved hydrogen content in the water sample, and the accurate measurement of the dissolved oxygen meter ensures the accuracy of the dissolved hydrogen measurement result, and the measurement result is not affected by the dissolved oxygen.
Description
Technical Field
The invention relates to a device and a method, in particular to a device and a method for measuring the content of dissolved hydrogen in high-temperature high-pressure steam, belonging to the technical field of overtemperature monitoring of the pipe walls of a superheater and a reheater of a power plant.
Background
For the metal material of the heating surface which runs for a long time under the actual working condition, the high-temperature oxidation condition of the heating surface is accurately monitored in real time, and the control of the oxidation speed measured by steam in a safe state is a key technology for preventing the superheater and the reheater from tube explosion. But the steam high-temperature oxidation of the superheater and the reheater is difficult to monitor on line, and the oxidation process can be represented only by indirect measurement. The change of the content of the dissolved hydrogen in the steam can be used for measuring the reaction speed between the high-temperature water steam and the inner walls of the superheater and the reheater. When local overheating occurs on the inner walls of the superheater and the reheater or an oxide layer begins to scale due to overheating, the content of dissolved hydrogen in steam will rise remarkably. The dissolved hydrogen content can reflect the actual conditions of the steam high-temperature oxidation of the superheater and the reheater, and is sensitive to the wall temperature index and the steam temperature index. However, in the actual use process, the measurement accuracy of the dissolved hydrogen meter is poor, and the measurement is particularly prominent when the boiler feed water is treated by oxygenation, so that the indicating effect of the dissolved hydrogen on the exceeding of the wall temperature is greatly weakened.
At present, dissolved hydrogen in main steam and reheated steam of a power plant is mainly measured by an online dissolved hydrogen meter, the meter has a similar working principle with a dissolved oxygen meter, and the meter is a testing technology based on a potential-current method. Under the condition of certain voltage, the current is in a linear relation with the dissolved hydrogen in the water sample. However, compared with the dissolved oxygen meter, the dissolved hydrogen meter adopting the potential current method has no definite inspection and calibration, and the measurement accuracy of the meter cannot be ensured.
At present, partial manufacturers check and calibrate the dissolved oxygen meter by adopting a standard gas method, but find that the measured value of the calibrated dissolved hydrogen meter has larger drift and poorer repeatability, and can not meet the requirement of measuring low-content dissolved hydrogen. On the other hand, some manufacturers use an electrolysis method for inspection and calibration, but the consistency of the electrolysis efficiency cannot be guaranteed, and the accuracy of a standard water sample cannot be guaranteed, so that the method is also controversial and cannot meet actual requirements.
At present, partial high-parameter and high-capacity generator sets are provided with main steam or reheated steam dissolved hydrogen meters, so that the on-line monitoring of dissolved hydrogen is realized, but the meters cannot be checked and calibrated, the validity of measurement data cannot be guaranteed, and the meters lose due effects. On the other hand, in the actual operation process, the measured value of the dissolved hydrogen meter is obviously influenced by the dissolved oxygen in the water sample, and the measured value of the dissolved hydrogen meter is particularly obvious in part of the oxygenating units, so that the measured value of the dissolved hydrogen meter is greatly changed, and the function of indicating that the wall temperature exceeds the standard cannot be achieved.
The invention discloses a method for measuring the hydrogen content in water of a boiler system and application thereof in Chinese patent with publication number CN106053673A of 2016, 26 and 10 months. The patent includes: (1) sampling from water in a boiler water vapor system to obtain a sample; (2) degassing the sample obtained in the step (1), and collecting to obtain equilibrium gas; (3) measuring the volume of the equilibrium gas, and measuring the concentration of hydrogen in the equilibrium gas obtained by degassing treatment by adopting a gas chromatography; (4) determining the dissolution coefficient of hydrogen in water through degassing treatment, and determining the original concentration of the dissolved hydrogen in the water of the boiler system according to the dissolution coefficient of hydrogen in water, the concentration of hydrogen in equilibrium gas, the equilibrium gas volume of the step (2) and the volume of the sample obtained in the step (1); the invention also relates to the use of the above method. The method adopts gas chromatography to analyze the dissolved hydrogen in the water, which is different from the method used in the application.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a device and a method for measuring the content of dissolved hydrogen in high-temperature high-pressure steam, the device has reasonable structural design, can simultaneously measure the content of dissolved oxygen and dissolved hydrogen in a water sample, can ensure the accuracy of a dissolved hydrogen measurement result by accurately measuring a dissolved oxygen meter, and can ensure that the measurement result is not influenced by the dissolved oxygen.
The technical scheme adopted by the invention for solving the problems is as follows: this dissolved hydrogen content measuring device in high temperature high pressure steam, including sample and the flow control unit that is used for controlling the water sample flow that awaits measuring, sample and flow control unit are including consecutive sampling tube way, needle valve and flowmeter, its characterized in that: the device comprises a sodium type resin column, a stainless steel tee joint, an injection pump, a desalting water tank, a dissolved oxygen meter flow cell, a palladium catalytic resin column, a dissolved oxygen meter and a programmable controller, wherein the sodium type resin column is connected with a sampling and flow control unit, the dissolved oxygen meter flow cell comprises a dissolved oxygen meter flow cell I and a dissolved oxygen meter flow cell II, one end of the stainless steel tee joint is connected with the sodium type resin column, the other two ends of the stainless steel tee joint are respectively connected with the dissolved oxygen meter flow cell I and an injection pump outlet, the other end of the injection pump is connected with the desalting water tank, the dissolved oxygen meter is connected with the dissolved oxygen meter flow cell through an electrode and an electrode wire, the injection pump is connected with the programmable controller through a signal wire, the palladium catalytic resin column is positioned between the two dissolved oxygen meter flow cells, the water discharged from the dissolved oxygen meter flow cell II enters a drainage tank of a unit, the two dissolved oxygen electrodes share one transmitter, the transmitter and the injection pump are connected with the programmable controller .
Preferably, the sodium type resin column is a sodium type cation exchange column, the sodium type resin column is arranged between the flowmeter and the stainless steel tee joint, the exchange column is made of organic glass, the sodium ion exchange resin is macroporous color-changing resin, the length of the exchange column is not less than 0.6m, the flow velocity of a water sample in the exchange column is not more than 18m/h, and an automatic exhaust valve is arranged at the top of the exchange column.
Preferably, the palladium catalytic resin column is arranged between the two dissolved oxygen flow tanks, the exchange column is made of organic glass, the length of the exchange column is not less than 0.6m, and the flow velocity of a water sample in the exchange column is not more than 18 m/h.
Preferably, the dissolved oxygen meter of the present invention has a working error of not more than 3.0. mu.g/L.
Preferably, the stainless steel tee joint and the desalting water tank are made of stainless steel, the volume of the desalting water tank is 100L, the injection pump comprises two independent infusion channels, the specification of the injector is not less than 50mL, and the two infusion channels are controlled by the programmable controller to be automatically switched and filled with liquid.
Preferably, the sampling pipeline outlet is positioned at the outlet of the high-temperature frame temperature and pressure reducer.
Preferably, the sampling pipeline and the needle valve are both made of stainless steel.
Preferably, the flowmeter is made of organic glass, and the measuring range of the flowmeter is 0L/h-30L/h.
Preferably, the programmable controller analyzes the content of the dissolved hydrogen according to the change value measured by the dissolved oxygen meter, and controls the start-stop and switching of the injection pump.
The invention also provides a method for measuring the content of dissolved hydrogen in high-temperature and high-pressure steam, which adopts the device for measuring the content of dissolved hydrogen in high-temperature and high-pressure steam, which is characterized in that: the method comprises the following steps: sampling from the outlet of the temperature and pressure reducer of the high-temperature sampling frame, and adjusting the flow of a water sample through a needle valve and a flowmeter; the water sample enters a sodium type resin column for ion exchange, and ammonia in the water sample is completely removed, so that ammonia poisoning of the subsequent palladium catalytic resin is avoided; at the stainless steel tee joint, the saturated oxygen demineralized water in the demineralized water tank is pumped into a water sample by an injection pump so as to improve the dissolved oxygen content of the water sample; when the oxygenated water sample flows through the palladium catalytic resin column, the dissolved oxygen and the dissolved hydrogen in the water sample react under the catalytic action of the palladium resin; detecting the content variation of dissolved oxygen before and after reaction by using dissolved oxygen meters before and after the palladium catalytic resin column; and the programmable controller outputs the content of the dissolved hydrogen in the water sample according to the measured value of the dissolved oxygen meter, thereby indicating whether the current superheater and the reheater are in an overtemperature state or not and giving corresponding warning signals.
Compared with the prior art, the invention has the following advantages and effects: (1) the method can simultaneously measure the content of the dissolved oxygen and the content of the dissolved hydrogen in the water sample, the dissolved oxygen meter can accurately measure the dissolved hydrogen, the accuracy of a dissolved hydrogen measurement result can be ensured, and the measurement result is not influenced by the dissolved oxygen; (2) a dissolved oxygen meter is used as a monitoring instrument, and the content of dissolved hydrogen is analyzed through the content change of dissolved oxygen before and after a palladium catalytic resin column, belonging to an indirect measurement method. Compared with the method of directly adopting a dissolved hydrogen meter, the method has the advantages that the dissolved oxygen meter measuring technology is more mature, the measuring accuracy is higher, and the dissolved oxygen meter based on optical emission basically does not need maintenance; (3) dissolved oxygen is used as a direct monitoring object, and the dissolved oxygen have a fixed relation of 8:1 in a catalytic reaction, so when the dissolved hydrogen content is analyzed by using a dissolved oxygen content change value, the error of the dissolved hydrogen is smaller, and only 1/8 of the measured value of a dissolved oxygen meter is obtained; (4) compared with a dissolved hydrogen meter, the dissolved oxygen meter has a mature metering calibration method and standard at present, has traceability and is more reliable in a dissolved hydrogen measurement result; (5) the measurement accuracy of dissolved hydrogen meter receives dissolved oxygen content influence in the water sample, nevertheless this application dissolved hydrogen content measuring device does not receive the dissolved oxygen content size influence in the steam in the high temperature high pressure steam.
Drawings
FIG. 1 is a schematic diagram of a device for measuring the content of dissolved hydrogen in high-temperature high-pressure steam according to an embodiment of the present invention.
In the figure: the system comprises a needle valve 1, a flowmeter 2, a sodium type resin column 3, a stainless steel tee joint 4, an injection pump 5, a demineralized water tank 6, a dissolved oxygen meter flow cell 7, a palladium catalytic resin column 8, a sampling pipeline 9, a dissolved oxygen meter 10, a programmable controller 11, a high-temperature frame temperature and pressure reducer 12, a unit water drainage tank 13, a dissolved oxygen meter flow cell I71 and a dissolved oxygen meter flow cell II 72.
Detailed Description
The present invention will be described in further detail below by way of examples with reference to the accompanying drawings, which are illustrative of the present invention and are not to be construed as limiting the present invention.
Examples are given.
Referring to fig. 1, the device for measuring the content of dissolved hydrogen in high-temperature and high-pressure steam in the embodiment includes a sampling and flow control unit for controlling the flow of a water sample to be measured, a sodium type resin column 3, a stainless steel tee joint 4, an injection pump 5, a desalting water tank 6, a dissolved oxygen meter flow cell 7, a palladium catalytic resin column 8, a dissolved oxygen meter 10 and a programmable controller 11, wherein the sampling and flow control unit includes a sampling pipeline 9, a needle valve 1 and a flowmeter 2 which are connected in sequence, the sodium type resin column 3 is connected with the sampling and flow control unit, the dissolved oxygen meter flow cell 7 includes a dissolved oxygen meter flow cell I71 and a dissolved oxygen meter flow cell II 72, one end of the stainless steel tee joint 4 is connected with the sodium type resin column 3, the other end of the stainless steel tee joint 4 is connected with the dissolved oxygen meter flow cell I71, one end of the injection pump 5 is connected with the stainless steel tee joint 4, the dissolved oxygen meter 10, the desalting water tank 6 is communicated with the injection pump 5, one end of the palladium catalytic resin column 8 is connected with a dissolved oxygen meter flow cell I71, the other end of the palladium catalytic resin column 8 is connected with a dissolved oxygen meter flow cell II 72, the water in the dissolved oxygen meter flow cell II 72 flows into the unit water drainage tank 13, and the programmable controller 11 is connected with the injection pump and the 5 dissolved oxygen meter 10 through signal lines.
The leading-out position of the sampling pipeline 9 of the embodiment is positioned at the outlet of the temperature and pressure reducing device 12 of the high-temperature frame; the sampling pipeline 9 and the needle valve 1 are both made of stainless steel; the flowmeter 2 is made of organic glass materials, and the measuring range of the flowmeter is 0L/h-30L/h.
The sodium type resin column 3 is a sodium type cation exchange column, the main function is to remove ammonia in a water sample and prevent palladium catalytic resin poisoning, the sodium type resin column 3 is installed behind the flowmeter 2 and in front of the stainless steel tee joint 4, the exchange column is made of organic glass, the sodium ion exchange resin is macroporous type color-changing resin, the length of the exchange column is not less than 0.6m, the flow rate of the water sample in the exchange column is not more than 18m/h, and the top of the exchange column is provided with an automatic exhaust valve.
The palladium catalytic resin column 8 is responsible for catalyzing the reaction of the dissolved hydrogen and the dissolved oxygen, the palladium catalytic resin column 8 is arranged between two dissolved oxygen flow cells, the exchange column is made of organic glass, the length of the exchange column is not less than 0.6m, and the flow velocity of a water sample in the exchange column is not more than 18 m/h; the exchange column is filled and compacted with palladium catalytic resin, and the water flow direction is downward inlet and upward outlet.
The dissolved oxygen meter 10 of the embodiment is an analysis and detection unit, is suitable for measuring low-content dissolved oxygen in ultrapure water, requires that the working error of the whole machine is not more than 3.0 mug/L, and is based on an optical method in the measurement principle.
The stainless steel tee joint 4, the injection pump 5 and the demineralized water tank 6 are auxiliary units of the measuring device, the installation position is located behind the sodium resin column 3 and in front of a first dissolved oxygen sensor, the stainless steel tee joint 4 and the demineralized water tank 6 are made of stainless steel, the volume of the demineralized water tank 6 is about 100L, the injection pump 5 comprises two independent infusion channels, the specification of the injector is not less than 50mL, and the two infusion channels can be automatically switched and filled with liquid under the control of the programmable controller 11.
Referring to fig. 1, the measuring device is used for measuring the water output from the high-temperature frame temperature and pressure reducer 12, and the water is generally superheated steam or reheated steam subjected to temperature and pressure reduction. The incoming water enters the needle valve 1 through a sampling pipe 9, and the sampling pipe 9 is required to be made of stainless steel materials, but cannot contain hydrogen absorption or hydrogen storage metals. The back of the needle valve 1 is connected with a float flowmeter 2 for measuring the water sample flow, and the water sample flow is controlled by adjusting the opening of the needle valve 1 to be about 20L/h.
The water sample enters the sodium type resin column 3 after the flow regulation, and all ammonia in the water sample is exchanged and removed, so that the subsequent palladium catalysis resin column 8 is prevented from generating ammonia poisoning and losing the catalytic activity. The top of the sodium type resin column 3 is provided with an automatic exhaust valve which can automatically remove the air bubbles in the water sample and eliminate the influence of the air bubbles on the measurement. The resin in the sodium resin column 3 adopts color-changing sodium ion exchange resin, and the state of the resin column can be judged according to the color change of the resin and the resin can be replaced in time.
In order to ensure that the content of dissolved oxygen in the water sample meets the requirement of complete reaction, the content of dissolved oxygen in the water sample needs to be ensured to be at least 10 times of the content of dissolved hydrogen. But in the unit that does not add oxygen or adopt low oxygen treatment, superheated steam or reheat steam's dissolved oxygen content is very low, can't satisfy the requirement, consequently sets up supplementary medicine unit, improves the dissolved oxygen content in the water sample. The auxiliary medicine adding unit consists of a double-channel injection pump 5 and a desalting water tank 6, the volume of the desalting water tank 6 is about 100L, the injection pump 5 continuously adds saturated oxygen desalting water into a water sample, and the dissolved oxygen content of the water sample is kept at least at 50 mug/L. The auxiliary medicine adding unit is connected with the main measuring flow path through a stainless steel tee joint 4, and the channel switching of the double-channel injection pump is jointly controlled by the programmable controller 11 and the injection pump 5.
A water sample passes through a stainless steel tee joint 4 and is added with drugs and then flows through a dissolved oxygen flow cell 7 and a palladium catalytic resin column 8 in sequence, and under the action of the palladium catalytic resin, dissolved oxygen and dissolved hydrogen in the water sample react in a fixed proportion to generate water; the dissolved hydrogen will react completely due to the excess amount of dissolved oxygen in the water sample.
Two dissolved oxygen flow cells 7 are arranged at the inlet and the outlet of the palladium catalytic resin column 8, and the dissolved oxygen content of inlet and outlet water of the palladium catalytic resin column 8 is monitored in real time.
In the embodiment, the dissolved oxygen meter 10 adopts an optical measurement principle, and the dissolved oxygen flow cell 7 is made of stainless steel; the two dissolved oxygen electrodes share one dissolved oxygen meter transmitter, the transmitter is connected with the programmable controller 11, and signals and data are transmitted between the two through 4-20mA current signals.
The programmable controller 11 of the embodiment is connected with the dissolved oxygen meter 10 and the injection pump 5, and controls the switching and starting and stopping of two channels of the injection pump 5 according to a set program; the programmable controller 11 receives the measurement result of the dissolved oxygen meter 10 and calculates according to an internal formula to give the content of dissolved hydrogen in the water sample, and then indicates whether the current superheater and reheater are in an overtemperature state or not according to the change trend of the content of dissolved hydrogen and gives a corresponding warning signal.
The steps for measuring the content of the dissolved hydrogen in the high-temperature high-pressure steam are as follows: sampling from the outlet of the temperature and pressure reducer of the high-temperature sampling frame, and adjusting the flow of a water sample through a needle valve 1 and a flowmeter 2; the water sample enters a sodium type resin column 3 for ion exchange, and ammonia in the water sample is completely removed, so that ammonia poisoning of the subsequent palladium catalytic resin is avoided; at the stainless steel tee joint 4, the injection pump 5 pumps saturated oxygen demineralized water in the demineralized water tank 6 into a water sample to improve the dissolved oxygen content of the water sample; when the oxygenated water sample flows through the palladium catalytic resin column 8, the dissolved oxygen and the dissolved hydrogen in the water sample react under the catalytic action of the palladium resin; dissolved oxygen table 10 in front of and behind palladium catalytic resin column 8 detects the amount of change in dissolved oxygen content before and after the reaction; the programmable controller 11 outputs the content of the dissolved hydrogen in the water sample according to the measured value of the dissolved oxygen meter 10, thereby indicating whether the current superheater and the reheater are in an overtemperature state or not and giving corresponding warning signals.
The whole measuring device can measure the content of dissolved oxygen and dissolved hydrogen in high-temperature high-pressure steam in real time, and can reflect the overtemperature condition of the pipe walls of the superheater and the reheater in time; in the whole measuring device, a sampling pipeline 9, a needle valve 1 and a flowmeter 2 form a sampling and flow control unit to ensure that the flow of a water sample is in a reasonable range; the sodium type resin column 3 is a preposed protection unit of the redox resin column, and is mainly used for removing ammonia in a water sample and preventing the redox resin column from generating ammonia poisoning and losing activity; the core unit of the palladium catalytic resin column 8 measuring device is responsible for catalyzing the reaction of the dissolved hydrogen and the dissolved oxygen; the stainless steel tee joint 4, the demineralized water tank 6 and the injection pump 5 are auxiliary units of the measuring device, demineralized water is added into an online water sample in real time to improve the content of dissolved oxygen, the content of dissolved oxygen in the water sample to be measured is not less than 10 times of the content of dissolved hydrogen, and the dissolved hydrogen is completely reacted in the palladium catalytic resin column 8; an auxiliary unit consisting of a demineralized water tank 6 and an injection pump 5 is connected with the main measuring flow path through a stainless steel tee joint 4; the dissolved oxygen meter 10 is a detection unit of the measuring device, and analyzes and detects the change of the dissolved oxygen in the water sample before and after the redox resin column; the dissolved oxygen meter 10 is used as a monitoring instrument, the meter is in double-channel configuration, and is connected with two dissolved oxygen electrodes and the dissolved oxygen flow cell 7. The dissolved oxygen flow cell 7 is respectively positioned behind the stainless steel tee joint 4 and the palladium catalytic resin column 8, and directly monitors the change of the dissolved oxygen content in the water sample in front of and behind the palladium catalytic resin column 8; the programmable controller 11 is an analysis and control unit of the measuring device, and the programmable controller 11 can receive signals of the dissolved oxygen meter 10 and the injection pump 5 at the same time, and analyze the content of the dissolved hydrogen in the water sample according to the measured value of the dissolved oxygen meter 10, thereby indicating whether the current superheater and the reheater are in an overtemperature state or not and giving corresponding warning signals. According to the signal of the injection pump 5, the programmable controller 11 controls the start, stop and switching of two injectors of the injection pump 5, and ensures that the two injectors are in a dosing state in real time.
The dissolved hydrogen content measuring device in the high-temperature high-pressure steam of the embodiment can be applied to the monitoring of the dissolved hydrogen content in the main steam, the reheated steam and the superheated steam of the power plant, can monitor the overtemperature condition of the pipe wall of the superheater and the reheater in real time, and has an important early warning effect on preventing the superheater and the reheater from being exploded.
And will be apparent to those skilled in the art from the foregoing description.
In addition, it should be noted that the specific embodiments described in the present specification may be different in the components, the shapes of the components, the names of the components, and the like, and the above description is only an illustration of the structure of the present invention. Equivalent or simple changes in the structure, characteristics and principles of the invention are included in the protection scope of the patent. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (10)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113567055A (en) * | 2021-06-30 | 2021-10-29 | 黔西县黔希煤化工投资有限责任公司 | Method for measuring leakage amount of process gas in steam heat exchanger |
| CN113984855A (en) * | 2021-10-22 | 2022-01-28 | 福建福清核电有限公司 | Method and device for measuring concentration of target gas in radioactive waste gas |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1309871A (en) * | 1971-03-01 | 1973-03-14 | North Hants Eng Co Ltd | Apparatus and method for monitoring of dissolved oxygen in a fluid |
| JPH06154511A (en) * | 1992-11-27 | 1994-06-03 | Toshiba Eng & Constr Co Ltd | Method for removing dissolved oxygen in water |
| CN1484019A (en) * | 2002-09-18 | 2004-03-24 | 中国科学院大连化学物理研究所 | An online trace oxygen content measurement method and special sensor |
| CN1699195A (en) * | 2004-05-20 | 2005-11-23 | 哈尔滨工业大学 | Process method for hydrogenation and deoxygenation of palladium ion catalyst resin |
| CN101038267A (en) * | 2007-04-13 | 2007-09-19 | 西安热工研究院有限公司 | Method and device for detecting flow injection type dissolved oxygen meter |
| US20110039348A1 (en) * | 2008-03-04 | 2011-02-17 | Seiji Katayama | Method of evaluating reaction between dissolved hydrogen and dissolved oxygen and method of evaluating ability of dissolved hydrogen to scavenge active oxygen in water |
| JP2011141234A (en) * | 2010-01-08 | 2011-07-21 | Japan Organo Co Ltd | Apparatus and method for measuring dissolved hydrogen concentration |
| KR20110131496A (en) * | 2010-05-31 | 2011-12-07 | 한국원자력기술 주식회사 | Hydrogen Monitoring System |
| CN106053673A (en) * | 2016-07-29 | 2016-10-26 | 神华集团有限责任公司 | Method for measuring hydrogen content in water of boiler system and application of method |
| JP2017020823A (en) * | 2015-07-08 | 2017-01-26 | 東西化学産業株式会社 | Dissolved hydrogen concentration measurement device and measuring method |
| CN109211309A (en) * | 2018-08-15 | 2019-01-15 | 国网陕西省电力公司电力科学研究院 | Hydrogen, micro- water and oil pressure comprehensive on-line monitoring apparatus are dissolved in oil-filled equipment oil |
| JP2019045349A (en) * | 2017-09-04 | 2019-03-22 | シャープ株式会社 | Dissolved hydrogen concentration measurement method |
| CN111007031A (en) * | 2019-12-26 | 2020-04-14 | 河南省日立信股份有限公司 | Method for measuring trace hydrogen or trace oxygen |
| CN212658669U (en) * | 2020-07-31 | 2021-03-05 | 华电电力科学研究院有限公司 | Device for measuring content of dissolved hydrogen in high-temperature and high-pressure steam |
-
2020
- 2020-07-31 CN CN202010762285.8A patent/CN112213439B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1309871A (en) * | 1971-03-01 | 1973-03-14 | North Hants Eng Co Ltd | Apparatus and method for monitoring of dissolved oxygen in a fluid |
| JPH06154511A (en) * | 1992-11-27 | 1994-06-03 | Toshiba Eng & Constr Co Ltd | Method for removing dissolved oxygen in water |
| CN1484019A (en) * | 2002-09-18 | 2004-03-24 | 中国科学院大连化学物理研究所 | An online trace oxygen content measurement method and special sensor |
| CN1699195A (en) * | 2004-05-20 | 2005-11-23 | 哈尔滨工业大学 | Process method for hydrogenation and deoxygenation of palladium ion catalyst resin |
| CN101038267A (en) * | 2007-04-13 | 2007-09-19 | 西安热工研究院有限公司 | Method and device for detecting flow injection type dissolved oxygen meter |
| US20110039348A1 (en) * | 2008-03-04 | 2011-02-17 | Seiji Katayama | Method of evaluating reaction between dissolved hydrogen and dissolved oxygen and method of evaluating ability of dissolved hydrogen to scavenge active oxygen in water |
| JP2011141234A (en) * | 2010-01-08 | 2011-07-21 | Japan Organo Co Ltd | Apparatus and method for measuring dissolved hydrogen concentration |
| KR20110131496A (en) * | 2010-05-31 | 2011-12-07 | 한국원자력기술 주식회사 | Hydrogen Monitoring System |
| JP2017020823A (en) * | 2015-07-08 | 2017-01-26 | 東西化学産業株式会社 | Dissolved hydrogen concentration measurement device and measuring method |
| CN106053673A (en) * | 2016-07-29 | 2016-10-26 | 神华集团有限责任公司 | Method for measuring hydrogen content in water of boiler system and application of method |
| JP2019045349A (en) * | 2017-09-04 | 2019-03-22 | シャープ株式会社 | Dissolved hydrogen concentration measurement method |
| CN109211309A (en) * | 2018-08-15 | 2019-01-15 | 国网陕西省电力公司电力科学研究院 | Hydrogen, micro- water and oil pressure comprehensive on-line monitoring apparatus are dissolved in oil-filled equipment oil |
| CN111007031A (en) * | 2019-12-26 | 2020-04-14 | 河南省日立信股份有限公司 | Method for measuring trace hydrogen or trace oxygen |
| CN212658669U (en) * | 2020-07-31 | 2021-03-05 | 华电电力科学研究院有限公司 | Device for measuring content of dissolved hydrogen in high-temperature and high-pressure steam |
Non-Patent Citations (3)
| Title |
|---|
| "氧中微量氢浓度分析仪", 化工自动化及仪表, no. 04, 30 August 1975 (1975-08-30) * |
| 孙吉星 冯雅琴: "《热工测量及显示仪表》", 31 July 1981, 电力工业出版社, pages: 100 * |
| 李海洋，王仁雷，尤良洲，衡世权: "溶解氧对主蒸汽溶解氢表测量影响试验研究", 华电科技, vol. 41, no. 7, 31 July 2019 (2019-07-31), pages 27 - 30 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113567055A (en) * | 2021-06-30 | 2021-10-29 | 黔西县黔希煤化工投资有限责任公司 | Method for measuring leakage amount of process gas in steam heat exchanger |
| CN113567055B (en) * | 2021-06-30 | 2024-05-28 | 黔西县黔希煤化工投资有限责任公司 | Method for measuring leakage amount of process gas in steam heat exchanger |
| CN113984855A (en) * | 2021-10-22 | 2022-01-28 | 福建福清核电有限公司 | Method and device for measuring concentration of target gas in radioactive waste gas |
| CN113984855B (en) * | 2021-10-22 | 2024-01-23 | 福建福清核电有限公司 | Method and device for measuring concentration of target gas in radioactive waste gas |
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