CN104880535A - Method for monitoring ammonia escape concentration - Google Patents
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- CN104880535A CN104880535A CN201510145542.2A CN201510145542A CN104880535A CN 104880535 A CN104880535 A CN 104880535A CN 201510145542 A CN201510145542 A CN 201510145542A CN 104880535 A CN104880535 A CN 104880535A
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Abstract
The present invention relates to the technical field of flue gas denitrification and provides a method for monitoring the ammoia escape concentration, which comprises the steps of S1, measuring the minimum nitrogen oxide (NOx) emission value at the exit of a reactor in the standard condition of ammoia escape; S2, monitoring the concentration of NOx at the exit of the reactor in an SCR system periodically or in real time. The measured concentration of NOx is compared with the minimum NOx emission value obtained during the step S1. If the minimum NOx concentration measured at the exit of the reactor in the SCR system during the operation process is not smaller than the minimum NOx emission value obtained during the step S1, the ammonia escape concentration is judged to meet the requirement. Otherwise, the ammonia escape concentration is judged not to meet the requirement. According to the above method for monitoring the ammoia escape concentration, the NOx concentration at the exit of the reactor in the SCR system is monitored and compared with the minimum NOx emission value in the standard condition of ammoia escape. In this way, the ammonia escape can be effectively monitored on line for directing the normal operation of the SCR system.
Description
Technical field
The present invention relates to gas denitrifying technology field, particularly relate to a kind of escape ammonia concentration monitoring method.
Background technology
Denitrating flue gas is the minimizing NO that current developed country generally adopts
xthe method of discharge, apply more selective catalytic reduction method (Selective catalytic reduction, be called for short SCR), SNCR method (Selective non-catalytic reduction, hereinafter referred to as SNCR), wherein the denitration rate of SCR is higher.The invention right of SCR belongs to the U.S., and Japan takes the lead in realizing its commercial applications in 20 century 70s.This technology has obtained in developed country and has applied more widely at present.Wherein, Japan has the denitrating flue gas of more than 93% to adopt SCR, and running gear is more than 300 covers; The power plant of China also generally adopts SCR technology to carry out denitration.Be described for system in Beijing Jing energy electric power incorporated company Shijingshan Power Plant, its fire coal boiler fume denitrating system adopts low NO in stove
xthe technical measures that burner combines with SCR (SCR).Wherein, the main technique occurred in SCR system has:
One) by the urea storage that ships outward in urea warehouse, be dissolved as 50% urea liquid by urea dissolving tank;
Two) in pyrolysis oven, above-mentioned urea liquid is evaporated to ammonia, and ammonia is sprayed in boiler by the nozzle of ammonia-spraying grid mixes with flue gas;
Three) static mixer sends into reactor after fully mixing ammonia, flue gas; When reaching temperature of reaction and with the well-mixed flue gas stream of ammonia when the Catalytic Layer of reactor, ammonia and NO
xgeneration catalytic oxidation-reduction reacts, by NO
xbe reduced to harmless N
2and H
2o.
In SCR denitration process, the amount of escape ammonia can be reduced by the straying quatity reducing ammonia, but can NO be caused simultaneously
xreduction transformation efficiency reduce.If the straying quatity of ammonia is too much, although can reduce NO
xdischarge, but have a large amount of the escaping of ammonia go out reaction zone formed escape ammonia, the SO that escape ammonia and denitration subsidiary reaction are produced
3react and generate ammonium hydrogen sulfate and ammonium sulfate, its reaction is as follows:
NH
3+SO
3+H
2O→NH
4HSO
4
2NH
3+SO
3+H
2O→(NH
4)
2SO
4
Because ammonium hydrogen sulfate has the character such as viscosity, hydroscopicity, once the too high resistance that will increase primary heater of ammonium hydrogen sulfate amount, the serious consequences such as primary heater blocks, fly-ash separator Electrode glues ash in a large number, electric field is closed, sack cleaner " paste bag " can be caused time serious, finally cause unit performance to reduce and even cannot run.
Research data shows, concentration and the ratio thereof of reactant are depended in the formation of ammonium hydrogen sulfate.The formation volume of ammonium hydrogen sulfate increases, high SO with the increase of escape ammonia concentration
3/ NH
3mol ratio is by the promotion formation of ammonium hydrogen sulfate and the deposition on primary heater thereof.The formation of ammonium hydrogen sulfate depends on temperature simultaneously, and when the initial formation temperature of flue-gas temperature a little less than ammonium hydrogen sulfate, namely ammonium hydrogen sulfate starts to be formed.When flue-gas temperature drops to the initial temperature 25 DEG C formed lower than ammonium hydrogen sulfate, ammonium hydrogen sulfate forming reactions can complete 95%.The definite forming region of ammonium hydrogen sulfate depends on initial formation temperature and the preheater temperature of ammonium hydrogen sulfate, and fluctuates at the axially lower of primary heater.
Under usual running temperature, the dew point of ammonium hydrogen sulfate is 147 DEG C, and it is assembled at body surface in liquid form or is scattered in flue gas with drops.Liquid ammonium hydrogen sulfate is the material that a kind of viscosity is very strong, can adhere to flying dust, cause flying dust degradation in flue gas, and recycle value reduces; Flying dust also can adhere to, corrode in air preheater, has a strong impact on the safety of primary heater, economy, stable operation.Ammonium hydrogen sulfate has hydroscopicity at low temperatures, if it is formed on the heat exchange element of primary heater, catalyst member can be caused to block, and increases catalyst pressure drop or causes catalyst failure.
In addition, escape ammonia itself is also one of air primary pollution source, if escape ammonia leaks in air can cause new pollution again.Clearly by ammonia and oxysulfide in " surrounding air fine particle integrated pollution control technical policy " that on September 13rd, 2013, Environmental Protection Department was issued, oxides of nitrogen, volatile organic matter (VOCs) etc. is classified as precursor pollutant together, and clearly " controlling the discharge behavior of various fine particle and precursor pollutant " is proposed comprehensively and strictly, " for the industrial pollution source of discharge precursor pollutant, removal oxysulfide should be adopted respectively, oxides of nitrogen, the Treatment process of volatile organic matter and ammonia ", " adopt ammonia as the purification of nitrogen oxides device of reductive agent, should under the prerequisite ensureing oxides of nitrogen qualified discharge, the filling technological parameter of ammonia is rationally set, prevent that ammonia is excessive to be polluted " etc. requirement.
Can predict, in SCR system, escape ammonia will become the key object of next environmental emission reduction and monitoring.Therefore, strictly must control the NH_3 leakage amount of SCR system, amount of ammonia slip be controlled at below 3ppm, prevent escape ammonia from causing secondary pollution to environment, reduce the escaping of ammonia to the harm of equipment.
In sum, at enforcement NO
xin the process reduced discharging, the Inspect and control of effective overall process is implemented also with regard to necessity very to escape ammonia.
Because the concentration of escape ammonia is extremely low, the disclosed online the escaping of ammonia monitoring technology of prior art generally adopts laser method, though online laser analyzer has sensing range advantage that is wide, that disturb without gas cross, but because laser penetration is poor, limit its use under high dust and high humidity environment, have impact on the Stability and veracity of escape ammonia Monitoring Data.
Again because the size of the concentration of escape ammonia in SCR system depends primarily on ammonia nitrogen mol ratio in the performance of denitrating catalyst self and SCR system, therefore prior art discloses a kind of method obtaining the amount of escape ammonia by detecting denitrating catalyst performance.The method is mainly on-site sampling at laboratory inspection test analysis.Although laboratory is complete to catalyst performance test item, testing result clear, accurately can reflect catalyst performance variation tendency, but be limited to and need to detect in laboratory conditions, it is only analyze catalyzer performance in laboratory conditions itself that catalyzer print detects, and can not reflect the actual performance of catalyzer in SCR system.
In view of this, a kind of effective escape ammonia concentration monitoring method newly is urgently proposed.
Summary of the invention
(1) technical matters that will solve
The technical problem to be solved in the present invention is just to provide a kind of new escape ammonia concentration monitoring method, realizes effective monitoring of escape ammonia.
(2) technical scheme
In order to solve the problems of the technologies described above, the invention provides a kind of escape ammonia concentration monitoring method, comprising the following steps:
The minimum nitrogen emissions of oxides value of S1, the reactor exit recorded under escape ammonia operating mode up to standard;
S2, reactor exit NO regularly or in Real-Time Monitoring SCR system
xconcentration, and the NO that will record
xthe described minimum nitrogen emissions of oxides value recorded in concentration and S1 contrasts, if the minimum NO that in SCR system operational process, reactor exit records
xconcentration is not less than the minimum nitrogen emissions of oxides value recorded in S1, then the concentration of escape ammonia meets the requirements; Otherwise then the concentration of escape ammonia is undesirable.
Preferably, described S1 comprises:
S11, on the outlet of detection reaction device, get several check points;
S12: the flue gas in boiler keeps imposing a condition, and progressively reduces the NO of reactor outlet in SCR system
xconcentration, and the escape ammonia concentration measuring check point position, until escape ammonia concentration reaches 3ppm;
S13: the NO recording corresponding check point
xconcentration value NO
x outlet 1, NO
x outlet 2, NO
x outlet 3, NO
x outlet 4
S14: to the NO of each check point obtained in S13
xconcentration value is analyzed, if the NO of all check points
xdeviation between concentration value drops in safe range, then calculate the NO of all check points
xthe mean value NO of concentration value
x exports mean value, described NO
x exports mean valuealso be the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard; If the NO of all check points
xdeviation between concentration value drops on outside safe range, then NO
outlet maximal valuefor the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard.
Preferably, in described S12, keep the NO of maximum continuous operating condition exhaust gas volumn, flue-gas temperature, reactor inlet in boiler
xconcentration stabilize, and the NH ensureing ground floor reactor inlet in SCR system
3/ NO
xmol ratio deviation ratio < 10%.
Preferably, the NO of all check points in described S14
xdeviation between concentration value drops in safe range and refers to NO
outlet mean valuewith NO
outlet maximal value, NO
outlet minimum valuelargest deviation be greater than 20%.
Preferably, the minimum nitrogen emissions of oxides value of the reactor exit under escape ammonia operating mode up to standard is manually recorded in described S1; Reactor exit NO in on-line monitoring SCR system in described S2
xconcentration.
Preferably, in described S2 to the NO of multiple check point position
xconcentration monitor.
(3) beneficial effect
Technical scheme of the present invention has the following advantages: escape ammonia concentration monitoring method of the present invention, by reactor exit NO in monitoring SCR system
xconcentration, and the minimum nitrogen emissions of oxides value under itself and escape ammonia operating mode up to standard to be contrasted, thus realizes the online effectively monitoring of escape ammonia, and then instruct the normal operation of SCR system.Further, by reactor exit NO in monitoring SCR system
xconcentration, the monitoring of denitrating catalyst performance can also be realized, for analysis and assessment catalyst performance provides a large amount of basic data and technical support.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schematic flow diagram of a kind of escape ammonia concentration monitoring method of the present invention.
Embodiment
Below in conjunction with drawings and Examples, embodiments of the present invention are described in further detail.Following examples for illustration of the present invention, but can not be used for limiting the scope of the invention.
The escape ammonia concentration monitoring method of the present embodiment, comprises the following steps:
The minimum nitrogen emissions of oxides value of S1, the reactor exit recorded under escape ammonia operating mode up to standard; Wherein, escape ammonia operating mode up to standard generally refers to that the concentration of ammonia is less than or equal to the situation of 3ppm;
S2, reactor exit NO regularly or in Real-Time Monitoring SCR system
xconcentration, and the NO that will record
xthe described minimum nitrogen emissions of oxides value recorded in concentration and S1 contrasts, if the minimum NO that in SCR system operational process, reactor exit records
xconcentration is not less than the minimum nitrogen emissions of oxides value recorded in S1, then the concentration of escape ammonia meets the requirements; Otherwise then the concentration of escape ammonia is undesirable.Wherein, minimum nitrogen emissions of oxides value is also SCR minimum safe discharge value.
In the present embodiment, by minimum nitrogen emissions of oxides value as the lower control limit value in SCR normal productive process.In normal productive process, minimum safe discharge value is not less than by reactor outlet NOx concentration value in production control system regulation and control SCR system, can meet the requirements (i.e. < 3ppm) by realization response device outlet ammonia slip concentration, namely control the normal reactor outlet NOx concentration value run in production run and can ensure that SCR exports ammonia slip concentration and meets the requirements higher than minimum safe discharge value.
In the present embodiment, S1 manually can record the minimum nitrogen emissions of oxides value of the reactor exit under escape ammonia operating mode up to standard, and this minimum nitrogen emissions of oxides value is a fixed numbers.S1 specifically can comprise the following steps:
S11, on the outlet of detection reaction device, get several check points;
S12: the flue gas in boiler keeps imposing a condition, and progressively reduces the NO of reactor outlet in SCR system
xconcentration, and the escape ammonia concentration measuring check point position, until escape ammonia concentration reaches 3ppm;
S13: the NO recording corresponding check point
xconcentration value NO
x outlet 1, NO
x outlet 2, NO
x outlet 3, NO
x outlet 4
S14: to the NO of each check point obtained in S13
xconcentration value is analyzed, if the NO of all check points
xdeviation between concentration value drops in safe range, then calculate the NO of all check points
xthe mean value NO of concentration value
x exports mean value, described NO
x exports mean valuealso be the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard.Now, NO
x outlet 1≈ NO
x outlet 2≈ NO
x outlet 3≈ NO
x outlet 4≈ NO
x exports mean value.If the NO of all check points
xdeviation between concentration value drops on outside safe range, then NO
outlet maximal valuefor the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard.Wherein, the minimum safe concentration of emission of the SCR system that minimum nitrogen emissions of oxides value is also namely tested.
Wherein, the deviation between the NOx concentration value of all check points of fruit drops in safe range and refers to: NO exports mean value and NO exports maximal value, NO goes out
mouth minimum valuelargest deviation > 20%; Otherwise, if NO
outlet mean valuewith NO
outlet maximal value, NO
outlet minimum valuelargest deviation < 20%, then the NO of all check points
xdeviation between concentration value drops on outside safe range.
Wherein, in S12, keep the NO of maximum continuous operating condition exhaust gas volumn, flue-gas temperature, reactor inlet in boiler
xconcentration stabilize, and the NH ensureing ground floor reactor inlet in SCR system
3/ NO
xmol ratio deviation ratio < 10%.
Preferably to reactor exit NO in SCR system in the present embodiment S2
xconcentration carry out on-line monitoring, the NO changed at any time
xconcentration value, and by minimum NO
xconcentration value and minimum nitrogen emissions of oxides value contrast, thus judge whether the concentration of escape ammonia meets the requirements, and control the input quantity of ammonia in SCR system according to judged result.
It is emphasized that can to the NO of multiple check point position in S2
xconcentration monitor, and pay close attention to the spray ammonia facility in region corresponding to the highest NOx concentration value, the state of ammonia/equipment such as flue gas mixing facility and catalyzer.When test result reflects that the limit denitration ability of same reactor exists severe deviations, should ascertain the reason as early as possible and eliminate.Further, SCR system should not in SCR system reactor exit NO
xconcentration lower than the operating mode of the minimum nitrogen emissions of oxides value recorded, or reactor exit NO in SCR system
xconcentration higher than long-play under operating mode corresponding to maximum denitration efficiency, to control or to slow down the negative effect of escape ammonia.
It is worth mentioning that, by reactor exit NO in monitoring SCR system
xconcentration, the monitoring of denitrating catalyst performance can also be realized, for analysis and assessment catalyst performance provides a large amount of basic data with technical support, coordinates.
Below in conjunction with specific experiment, the present embodiment is described:
One, pacing items is tested:
Boiler runs under being in the maximum continuous operating condition exhaust gas volumn condition of stable state; Boiler smoke temperature, furnace exit temperature, Oxygen Amount in Flue Gas meet SCR designing requirement, and amplitude of variation≤5%; SCR ground floor reactor inlet NH3/NOx mol ratio deviation ratio≤10%; Denitrification reducing agent feed system is stable.
Two, reference standard is tested:
1, DL/T260-2012 coal-fired plant flue gas denitrification apparatus performances acceptance test specification Appendix B
2, in GB/T 16157-1996 Concentration in Fixed Pollutants Source, particle measures and the gaseous contaminant method of sampling
Three, main experimental instrument
Ammonia gas-sensing electrode: 9512HPBNWP, Thermo;
Multi parameter analysis instrument: Orion 5star, Thermo;
Magnetic stirring apparatus: RT5, IKA;
Moral figure testo350pro flue gas analyzer.
Four, testing procedure
Refer to Fig. 1, it embodies the idiographic flow of test.
Successful utilization is in Shijingshan Power Plant for the escape ammonia concentration monitoring method of the present embodiment, and through long period application verification, this monitoring method can ensure that set is stable, reliable, and the effect that is suitable for of the method meets the target of expecting and setting up completely.
Above embodiment is only for illustration of the present invention, but not limitation of the present invention.Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, various combination, amendment or equivalent replacement are carried out to technical scheme of the present invention, do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of right of the present invention.
Claims (6)
1. an escape ammonia concentration monitoring method, is characterized in that, comprises the following steps:
The minimum nitrogen emissions of oxides value of S1, the reactor exit recorded under escape ammonia operating mode up to standard;
S2, reactor exit NO regularly or in Real-Time Monitoring SCR system
xconcentration, and the NO that will record
xthe described minimum nitrogen emissions of oxides value recorded in concentration and S1 contrasts, if the minimum NO that in SCR system operational process, reactor exit records
xconcentration is not less than the minimum nitrogen emissions of oxides value recorded in S1, then the concentration of escape ammonia meets the requirements; Otherwise then the concentration of escape ammonia is undesirable.
2. method according to claim 1, is characterized in that, described S1 comprises:
S11, on the outlet of detection reaction device, get several check points;
S12: the flue gas in boiler keeps imposing a condition, and progressively reduces the NO of reactor outlet in SCR system
xconcentration, and the escape ammonia concentration measuring check point position, until escape ammonia concentration reaches 3ppm;
S13: the NO recording corresponding check point
xconcentration value NO
x outlet 1, NO
x outlet 2, NO
x outlet 3, NO
x outlet 4
S14: to the NO of each check point obtained in S13
xconcentration value is analyzed, if the NO of all check points
xdeviation between concentration value drops in safe range, then calculate the NO of all check points
xthe mean value NO of concentration value
x exports mean value, described NO
x exports mean valuealso be the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard; If the NO of all check points
xdeviation between concentration value drops on outside safe range, then NO
outlet maximal valuefor the minimum nitrogen emissions of oxides value under escape ammonia operating mode up to standard.
3. method according to claim 2, is characterized in that, in described S12, keeps the NO of maximum continuous operating condition exhaust gas volumn, flue-gas temperature, reactor inlet in boiler
xconcentration stabilize, and the NH ensureing ground floor reactor inlet in SCR system
3/ NO
xmol ratio deviation ratio < 10%.
4. method according to claim 2, is characterized in that, the NO of all check points in described S14
xdeviation between concentration value drops in safe range and refers to NO
outlet mean valuewith NO
go out mouth maximal value, NO
outlet minimum valuelargest deviation be greater than 20%.
5. method according to claim 1, is characterized in that, manually records the minimum nitrogen emissions of oxides value of the reactor exit under escape ammonia operating mode up to standard in described S1; Reactor exit NO in on-line monitoring SCR system in described S2
xconcentration.
6. method according to claim 1, is characterized in that, to the NO of multiple check point position in described S2
xconcentration monitor.
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|---|---|---|---|
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| CN106295166A (en) * | 2016-08-05 | 2017-01-04 | 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 application thereof |
| CN108645964A (en) * | 2018-04-23 | 2018-10-12 | 华北电力科学研究院有限责任公司 | The equal values determination method of SCR denitration device the escaping of ammonia based on carbamide reducing agent and system |
| 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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| CN104880535B (en) | 2020-02-04 |
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Effective date of registration: 20180412 Address after: 072750 Zhuozhou City, Hebei Province, East Xian Po Town Applicant after: HEBEI ZHUOZHOU JINGYUAN THERMAL ELECTRICITY CO., LTD. Address before: 100041 Guangning Road, Shijingshan District, Shijingshan District, Beijing Applicant before: SHIJINGSHAN THERMOELETRIC PLANT, BEIJING JINGNENG POWER CO., LTD. |
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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. |