CN104880535B - Method for monitoring concentration of escaped ammonia - Google Patents
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Abstract
The invention relates to the technical field of flue gas denitration, and provides an escaping ammonia concentration monitoring method, which comprises the following steps: s1, measuring the minimum nitrogen oxide emission value at the outlet of the reactor under the standard-reaching working condition of the escaped ammonia; s2, monitoring NO at outlet of reactor in SCR system periodically or in real timexAnd will measureObtained NOxComparing the concentration with the minimum NOx emission value measured in S1 if the minimum NO measured at the reactor outlet during operation of the SCR systemxThe concentration is not less than the minimum nitrogen oxide emission value measured in S1, the concentration of the escaped ammonia meets the requirement; otherwise, the concentration of the escaped ammonia is not satisfactory. The method for monitoring the concentration of the escaped ammonia is realized by monitoring NO at the outlet of a reactor in an SCR systemxThe concentration of the ammonia gas is compared with the minimum nitrogen oxide emission value under the standard-reaching working condition of the escaped ammonia, so that the escaped ammonia is effectively monitored on line, and the normal operation of the SCR system is guided.
Description
Technical Field
The invention relates to the technical field of flue gas denitration, in particular to a method for monitoring the concentration of escaping ammonia.
Background
Flue gas denitration is commonly adopted in developed countries at present for reducing NOxThe emission method is characterized in that Selective Catalytic Reduction (SCR) and Selective non-catalytic reduction (SNCR) are applied, wherein the denitration rate of the SCR is high. The invention of SCR belongs to the united states, and the japan rate achieved its commercial application prior to the 70's of the 20 th century. The technology is widely applied in developed countries at present. Wherein, more than 93 percent of smoke denitration in Japan adopts SCR, and the number of running devices exceeds 300; the SCR technology is also commonly adopted in the power plants in China for denitration. Taking the stone mountain thermal power plant of Beijing energy electric power company Limited as an example for explanation, the flue gas denitration system of the coal-fired boiler adopts the in-furnace low NOxBurner and SCR (selective catalytic reduction) combined technical measures. Among the major processes that occur in SCR systems are:
firstly), storing the transported urea in a urea storage bin, and dissolving the urea into a 50% urea solution through a urea dissolving tank;
secondly), evaporating the urea solution into ammonia gas in a pyrolysis furnace, and spraying the ammonia gas into the boiler through a nozzle of an ammonia spraying grid to be mixed with the flue gas;
thirdly), the static mixer fully mixes the ammonia gas and the flue gas and then sends the mixture into the reactor; when the flue gas which reaches the reaction temperature and is fully mixed with the ammonia flows through the catalyst layer of the reactor, the ammonia and NOxCatalytic oxidation-reduction reaction is carried out to react NOxReduction to harmless N2And H2O。
During SCR denitration, the amount of ammonia slip can be reduced by reducing the ammonia injection amount, but the ammonia slip can also cause NOxThe reductive conversion efficiency of (2) is decreased. If the injected amount of ammonia is excessive, NO can be reducedxBut a large amount of ammonia escapes from the reaction zone to form escaped ammonia which is reacted with SO produced by denitration side reaction3The reaction takes place to form ammonium bisulfate and ammonium sulfate, which are reacted as follows:
NH3+SO3+H2O→NH4HSO4
2NH3+SO3+H2O→(NH4)2SO4
because ammonium bisulfate has properties such as viscosity and hygroscopicity, once the ammonium bisulfate is excessively high, the resistance of the preheater can be increased, serious consequences such as blockage of the preheater, large amount of sticky ash on electric field polar plates of the dust remover, closed electric field, bag pasting of the bag type dust remover and the like can be caused in serious cases, and finally, the performance of the unit is reduced or even the unit cannot operate.
Research data show that the formation of ammonium bisulfate depends on the concentration of the reactants and their ratio. The formation amount of ammonium bisulfate increases along with the increase of the concentration of escaping ammonia, and the SO is high3/NH3The molar ratio will promote the formation of ammonium bisulfate and its deposition on the preheater. The formation of ammonium bisulfate is simultaneously temperature dependent, and ammonium bisulfate begins to form when the flue gas temperature is slightly below the initial formation temperature of ammonium bisulfate. When the temperature of the flue gasThe ammonium bisulfate formation reaction can be 95% complete when the temperature drops below the initial ammonium bisulfate formation temperature by 25 ℃. The exact formation zone of ammonium bisulfate depends on the initial formation temperature of ammonium bisulfate and the preheater temperature and fluctuates up and down in the axial direction of the preheater.
At typical operating temperatures, ammonium bisulfate has a dew point of 147 ℃, and is collected on the surface of the object in liquid form or dispersed in the flue gas in the form of droplets. The liquid ammonium bisulfate is a substance with strong viscosity, and can be adhered to fly ash in flue gas, so that the quality of the fly ash is deteriorated, and the recycling value is reduced; the fly ash can also adhere to and corrode the inside of the air preheater, and the safe, economical and stable operation of the preheater is seriously influenced. Ammonium bisulfate is hygroscopic at low temperatures and, if it forms on the heat exchange elements of the preheater, can cause partial plugging of the catalyst, increase catalyst pressure drop or cause catalyst failure.
In addition, the escaped ammonia is one of the main pollution sources of the atmosphere, and if the escaped ammonia leaks into the atmosphere, new pollution is caused. In the technical policy of comprehensive prevention and control of environmental air fine particulate matter pollution issued by the ministry of environmental protection at 9/13/2013, ammonia, sulfur oxides, nitrogen oxides, Volatile Organic Compounds (VOCs) and the like are listed as precursor pollutants, and the requirements of comprehensively and strictly controlling the discharge behaviors of various fine particulate matters and precursor pollutants, adopting a treatment technology for removing sulfur oxides, nitrogen oxides, volatile organic compounds and ammonia for an industrial pollution source for discharging the precursor pollutants, reasonably setting ammonia filling technological parameters and preventing pollution caused by excessive ammonia on the premise of ensuring that the nitrogen oxides reach the discharge standard, and the like are clearly proposed.
It is expected that ammonia escaping from the SCR system will be a key object for the next environmental protection, emission reduction and monitoring. Therefore, the ammonia leakage amount of the SCR system must be strictly controlled, the ammonia escape amount is controlled to be less than 3ppm, secondary pollution to the environment caused by the escaped ammonia is prevented, and the harm of the escaped ammonia to equipment is reduced.
In summary, in the practice of NOxIn the process of emission reduction, effective completion is carried out on escaping ammoniaMonitoring and control of the process is also necessary.
Because the concentration of the escaped ammonia is extremely low, the online ammonia escape monitoring technology disclosed by the prior art generally adopts a laser method, and although an online laser analyzer has the advantages of wide detection range and no gas cross interference, the use of the online laser analyzer in high-dust and high-humidity environments is limited due to poor laser penetrability, and the accuracy and stability of escaped ammonia monitoring data are influenced.
Since the concentration of the ammonia slip in the SCR system mainly depends on the performance of the denitration catalyst itself and the molar ratio of ammonia to nitrogen in the SCR system, the prior art discloses a method for obtaining the amount of ammonia slip by detecting the performance of the denitration catalyst. The method mainly comprises the steps of sampling on site, and testing, testing and analyzing in a laboratory. Although the laboratory has complete catalyst performance detection items, and the detection result can clearly and accurately reflect the catalyst performance change trend, the detection is limited to be carried out under the laboratory condition, and the catalyst sample wafer detection only analyzes the performance of the catalyst under the laboratory condition and cannot reflect the actual performance of the catalyst in the SCR system.
In view of the above, a new effective method for monitoring the concentration of ammonia slip is needed.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a novel method for monitoring the concentration of escaping ammonia, so as to realize effective monitoring of the escaping ammonia.
(II) technical scheme
In order to solve the technical problem, the invention provides a method for monitoring the concentration of escaped ammonia, which comprises the following steps:
s1, measuring the minimum nitrogen oxide emission value at the outlet of the reactor under the standard-reaching working condition of the escaped ammonia;
s2, monitoring NO at outlet of reactor in SCR system periodically or in real timexAnd measured NO is measuredxComparing the concentration with the minimum nitrogen oxide emission value measured in S1 if the concentration is the highest measured at the reactor outlet during the operation of the SCR systemSmall NOxThe concentration is not less than the minimum nitrogen oxide emission value measured in S1, the concentration of the escaped ammonia meets the requirement; otherwise, the concentration of the escaped ammonia is not satisfactory.
Preferably, the S1 includes:
s11, taking a plurality of detection points on the outlet section of the detection reactor;
s12: the flue gas in the boiler keeps set conditions, and the NO at the outlet of the reactor in the SCR system is gradually reducedxMeasuring the concentration of the escaped ammonia at the position of the detection point until the concentration of the escaped ammonia reaches 3 ppm;
s13: recording NO of corresponding detection pointxConcentration value NOx outlet 1、NOx outlet 2、NOx outlet 3、NOx outlet 4……；
S14: NO at each detection point obtained in S13xAnalyzing the concentration value if NO is detected at all pointsxIf the deviation between the concentration values falls within a safe range, the NO values at all the detection points are calculatedxMean value of concentration values NOAverage value of x outletSaid NOAverage value of x outletNamely the minimum nitrogen oxide emission value under the standard working condition of the escaped ammonia; if all the detected points are NOxDeviation between concentration values falling outside the safety range, NOMaximum value of outletThe emission value of the nitrogen oxides is the minimum emission value of the nitrogen oxides under the standard working condition of the escaped ammonia.
Preferably, in the step S12, the maximum continuous operation condition flue gas quantity, the flue gas temperature and the NO at the inlet of the reactor in the boiler are maintainedxThe concentration is stable, and NH at the inlet of a first layer reactor in an SCR system is ensured3/NOxThe molar deviation is less than 10%.
Preferably, NO at all detection points in S14xDeviation between concentration values falling within a safe range means NOOutlet mean valueWith NOMaximum value of outlet、NOExit minimumIs greater than 20%.
Preferably, in the step S1, the minimum nitrogen oxide emission value at the outlet of the reactor under the standard condition of the escaped ammonia is manually measured; in-line monitoring SCR in S2NO at the reactor outlet in the systemxThe concentration of (c).
Preferably, the NO at the plurality of detection point positions in S2xIs monitored.
(III) advantageous effects
The technical scheme of the invention has the following advantages: the method for monitoring the concentration of the escaped ammonia is realized by monitoring NO at the outlet of a reactor in an SCR systemxThe concentration of the ammonia gas is compared with the minimum nitrogen oxide emission value under the standard-reaching working condition of the escaped ammonia, so that the escaped ammonia is effectively monitored on line, and the normal operation of the SCR system is guided. Further, by monitoring NO at the outlet of the reactor in the SCR systemxThe concentration of the denitration catalyst can also realize the monitoring of the performance of the denitration catalyst, and provide a large amount of basic data and technical support for evaluating and analyzing the performance of the catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a slip ammonia concentration monitoring method of the present invention.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The method for monitoring the concentration of the escaped ammonia comprises the following steps:
s1, measuring the minimum nitrogen oxide emission value at the outlet of the reactor under the standard-reaching working condition of the escaped ammonia; wherein, the standard-reaching working condition of the escaped ammonia generally refers to the condition that the concentration of the ammonia is less than or equal to3 ppm;
s2, monitoring NO at outlet of reactor in SCR system periodically or in real timexThe concentration of (a) in (b),and measured NOxComparing the concentration with the minimum NOx emission value measured in S1 if the minimum NO measured at the reactor outlet during operation of the SCR systemxThe concentration is not less than the minimum nitrogen oxide emission value measured in S1, the concentration of the escaped ammonia meets the requirement; otherwise, the concentration of the escaped ammonia is not satisfactory. Wherein the minimum nitrogen oxide emission value is also the minimum safe emission value of SCR.
In this embodiment, the minimum nox emission value is used as the lower limit value for controlling the SCR normal production process. In the normal production process, the concentration value of NOx at the outlet of the reactor in the SCR system is regulated and controlled by the production control system to be not lower than the minimum safe emission value, so that the ammonia escape concentration at the outlet of the reactor meets the requirement (namely, is less than 3ppm), namely, the concentration value of NOx at the outlet of the reactor in the normal operation production process is controlled to be higher than the minimum safe emission value, so that the ammonia escape concentration at the outlet of the SCR can meet the requirement.
In this embodiment, S1 may be implemented by manually measuring the minimum nox emission value at the outlet of the reactor under the standard condition of the escaped ammonia, where the minimum nox emission value is a fixed value. S1 may specifically include the following steps:
s11, taking a plurality of detection points on the outlet section of the detection reactor;
s12: the flue gas in the boiler keeps set conditions, and the NO at the outlet of the reactor in the SCR system is gradually reducedxMeasuring the concentration of the escaped ammonia at the position of the detection point until the concentration of the escaped ammonia reaches 3 ppm;
s13: recording NO of corresponding detection pointxConcentration value NOx outlet 1、NOx outlet 2、NOx outlet 3、NOx outlet 4……；
S14: NO at each detection point obtained in S13xAnalyzing the concentration value if NO is detected at all pointsxIf the deviation between the concentration values falls within a safe range, the NO values at all the detection points are calculatedxMean value of concentration values NOAverage value of x outletSaid NOAverage value of x outletNamely the minimum nitrogen oxide emission value under the standard working condition of the escaped ammonia. At this time, NOx outlet1≈NOx outlet 2≈NOx outlet 3≈NOx outlet 4……≈NOAverage value of x outlet. If all the detected points are NOxDeviation between concentration values falling outside the safety range, NOMaximum value of outletThe emission value of the nitrogen oxides is the minimum emission value of the nitrogen oxides under the standard working condition of the escaped ammonia. Wherein the minimum nox emission value is also the minimum safe emission concentration of the SCR system being tested.
Wherein if the deviation between the NOx concentration values at all the detection points falls within a safe range means: mean value of NO outlet and maximum value of NO outlet, NO outletMouth minimumThe maximum deviation rate is more than 20 percent; on the contrary, if NOOutlet mean valueWith NOMaximum value of outlet、NOExit minimumMaximum deviation < 20%, NO at all detection pointsxThe deviation between the concentration values falls outside the safety range.
Wherein in S12, the maximum continuous operation working condition flue gas volume, flue gas temperature and NO at the inlet of the reactor in the boiler are maintainedxThe concentration is stable, and NH at the inlet of a first layer reactor in an SCR system is ensured3/NOxThe molar deviation is less than 10%.
This example S2 is preferably applied to the NO at the outlet of the reactor in the SCR systemxThe concentration of the nitric oxide is monitored on line to obtain NO which changes at any timexAnd minimum NO concentration valuexAnd comparing the concentration value with the minimum nitrogen oxide emission value to judge whether the concentration of the escaped ammonia meets the requirement or not, and controlling the input amount of the ammonia in the SCR system according to the judgment result.
It is emphasized that NO at S2 can be detected for a plurality of positions of the detection pointxAnd the concentration of the NOx is monitored, and the states of equipment such as an ammonia spraying facility, an ammonia/flue gas mixing facility, a catalyst and the like in the area corresponding to the highest NOx concentration value are focused. When the test results reflect that there is a serious deviation in the ultimate denitrification capacity of the same reactor, the cause should be identified and eliminated as soon as possible. Also, the SCR system should not have NO at the reactor outlet in the SCR systemxIs below the measured minimum nitrogen oxide emission value, or NO at the reactor outlet in an SCR systemxIs rich inThe working condition corresponding to the denitration efficiency is higher than the maximum denitration efficiency, and the operation is carried out for a long time so as to control or slow down the negative influence of escaping ammonia.
It is worth mentioning that by monitoring NO at the reactor outlet in the SCR systemxThe concentration of the denitration catalyst can also realize the monitoring of the performance of the denitration catalyst, and provide a large amount of basic data, technical support and matching for evaluating and analyzing the performance of the catalyst.
This example is illustrated below with reference to specific experiments:
firstly, basic test conditions:
the boiler is operated under the condition of the maximum steady-state continuous operation working condition smoke gas volume; the temperature of the boiler flue gas, the temperature of the hearth outlet and the oxygen content of the flue gas meet the design requirements of SCR, and the variation range is less than or equal to 5 percent; the deviation rate of the NH3/NOx molar ratio at the inlet of the SCR first layer reactor is less than or equal to 10 percent; denitration reductant feed system operates steadily.
II, test reference standard:
1. DL/T260-2012 coal-fired power plant flue gas denitration device performance acceptance test specification appendix B
2. Method for measuring particulate matters in exhaust gas of GB/T16157-1996 fixed pollution source and sampling gaseous pollutants
Three, main test instrument
Ammonia gas sensitive electrode: 9512HPBNWP, Thermo;
a multi-parameter analyzer: orion 5star, Thermo;
a magnetic stirrer: RT5, IKA;
deuttig 350pro smoke analyser.
Fourthly, testing steps
Please refer to fig. 1, which shows a specific flow of the test.
The method for monitoring the concentration of the escaped ammonia is successfully applied to the thermal power plant in the rocky mountain, and the monitoring method can ensure that the unit device is stable and reliable after long-period application and inspection, and the application effect of the method completely meets the expected set target.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (5)
1. A method for monitoring the concentration of escaped ammonia is characterized by comprising the following steps:
s1, measuring the minimum nitrogen oxide emission value at the outlet of the reactor under the standard-reaching working condition of the escaped ammonia;
s2, monitoring NO at outlet of reactor in SCR system periodically or in real timexAnd measured NO is measuredxComparing the concentration with the minimum NOx emission value measured in S1 if the minimum NO measured at the reactor outlet during operation of the SCR systemxThe concentration is not less than the minimum nitrogen oxide emission value measured in S1, the concentration of the escaped ammonia meets the requirement; otherwise, the concentration of the escaped ammonia does not meet the requirement; the S1 includes:
s11, taking a plurality of detection points on the outlet section of the detection reactor;
s12: the flue gas in the boiler keeps set conditions, and the NO at the outlet of the reactor in the SCR system is gradually reducedxMeasuring the concentration of the escaped ammonia at the position of the detection point until the concentration of the escaped ammonia reaches 3 ppm;
s13: recording NO of corresponding detection pointxConcentration value NOx outlet 1、NOx outlet 2、NOx outlet 3、NOx outlet 4……；
S14: NO at each detection point obtained in S13xAnalyzing the concentration value if NO is detected at all pointsxIf the deviation between the concentration values falls within a safe range, the NO values at all the detection points are calculatedxMean value of concentration values NOAverage value of x outletSaid NOAverage value of x outletNamely the minimum nitrogen oxide emission value under the standard working condition of the escaped ammonia; if all the detected points are NOxDeviation between concentration values falling outside the safety range, NOMaximum value of outletMinimum nitrogen oxide under standard working condition for escaping ammoniaA value of emissions.
2. The method according to claim 1, wherein in S12, the maximum continuous operation flue gas quantity, the flue gas temperature and the NO at the inlet of the reactor in the boiler are maintainedxThe concentration is stable, and NH at the inlet of a first layer reactor in an SCR system is ensured3/NOxThe molar deviation is less than 10%.
3. The method of claim 1, wherein NO at all detection points in S14xDeviation between concentration values falling within a safe range means NOOutlet mean valueWith NOMaximum value of outlet、NOExit minimumIs greater than 20%.
4. The method of claim 1, wherein the minimum nitrogen oxide emission value at the reactor outlet under the slip ammonia standard condition is manually measured in S1; in S2, NO at outlet of reactor in SCR system is monitored on linexThe concentration of (c).
5. The method of claim 1, wherein the NO at S2 for multiple locations of detection pointsxIs monitored.
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| CN105854595A (en) * | 2016-05-12 | 2016-08-17 | 江苏龙净科杰催化剂再生有限公司 | Method for debugging SCR (selective catalytic reduction) flue gas denitrification device |
| CN106295166B (en) * | 2016-08-05 | 2018-06-05 | 国网安徽省电力公司电力科学研究院 | A kind of SCR denitration device amount of ammonia slip measuring method and its application |
| CN108645964B (en) * | 2018-04-23 | 2020-11-06 | 华北电力科学研究院有限责任公司 | Method and system for measuring ammonia escape mean value of SCR (Selective catalytic reduction) denitration device based on urea reducing agent |
| CN112727580A (en) * | 2019-10-28 | 2021-04-30 | 沪东重机有限公司 | Working time sequence-based NOx sensor calibration method |
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| CN102759931B (en) * | 2012-08-03 | 2015-09-02 | 北京华能新锐控制技术有限公司 | The control method of denitrating flue gas and device |
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Effective date of registration: 20200804 Address after: 072750, Baoding, Hebei province Zhuozhou City East cents slope town Co-patentee after: Beijing Jingneng Electric Power Co.,Ltd. Patentee after: HEBEI ZHUOZHOU JINGYUAN THERMAL ELECTRICITY Co.,Ltd. Address before: 072750 Zhuozhou City, Hebei Province, East Xian Po Town Patentee before: HEBEI ZHUOZHOU JINGYUAN THERMAL ELECTRICITY Co.,Ltd. |