CN106526064B - A kind of method of catalyst activity during dynamic detection SCR denitration - Google Patents
A kind of method of catalyst activity during dynamic detection SCR denitration Download PDFInfo
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- CN106526064B CN106526064B CN201611033153.1A CN201611033153A CN106526064B CN 106526064 B CN106526064 B CN 106526064B CN 201611033153 A CN201611033153 A CN 201611033153A CN 106526064 B CN106526064 B CN 106526064B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 230000000694 effects Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- 239000003546 flue gas Substances 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims description 5
- 235000019504 cigarettes Nutrition 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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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- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The method that the present invention discloses catalyst activity during a kind of dynamic detection SCR denitration, includes the following steps：(1) the flue gas flow L at a certain moment denitration reactor inlet is measured1, NO in flue gasXConcentration Dn1And the flue gas flow L in exit2With NO in the flue gas of exitXConcentration Dn2；(2) the ammonia flow L at the moment denitration reactor inlet is measuredA, ammonia concentration An1And the ammonia concentration A in exitn2；(3) catalyst activity percentage K, the K=[L at the moment are calculated1*Dn1‑L2*Dn2]/[Dn1*L1*K1*K2*K3+(An2‑An4lx)*L2]；Wherein, K1、K2、K3Characterization Benitration reactor inside oxygen content, ammonia amount and Benitration reactor internal temperature are to the impact factor of catalyst denitration reaction, K respectively1、K2、K3Respectively less than it is equal to 1；An4lxAllow the ammonia concentration of discharge for Benitration reactor exit.The method of the present invention can detect that the real-time activity of catalyst in denitrification process ensures the high efficiency of denitrification process to instruct staff's more catalyst changeout in time.
Description
Technical field
The present invention relates to a kind of detection method of catalyst activity, more particularly to during a kind of dynamic detection SCR denitration
The method of catalyst activity.
Background technology
Coal-burning installation, such as thermal power plant, it is NOx that discharge flue gas, which can cause atmosphere pollution, one of major pollutants, existing
The most ripe gas denitrifying technology of some is selective catalytic reduction (SCR), using reducing agent (ammonia, urea) in catalyst
Under effect, selectively with NOx, reaction generate N2And H2O。
Catalyst is the core component of SCR denitration system, accounts for the 30%-50% or so entirely invested.General catalyst makes
The phenomenon that just will appear inactivation or activity reduction with 1-2 or so.During denitration reaction, due to fuel, equipment and operation etc.
The activity of the reason of aspect, catalyst can constantly decline, arsenic, alkali metal, alkaline-earth metal and the metal oxidation being such as present in coal
Object etc., when flue-gas temperature declines, on a catalyst, it is anti-with the acid centre in catalyst chemistry may to occur for meeting coagulating sedimentation
It answers, destroys the activity of catalyst；Temperature fluctuation can also cause catalyst activity to reduce the physical damnification of catalyst in flue gas.Together
When limited by coal market supply conditions, it is larger actually to use coal off-design value, to ensure denitration efficiency, to SCR systems
More stringent requirements are proposed for the operation and maintenance of system catalyst.
Generally using the hours of operation of catalyst as catalyst chemical service life, after reaching projected life, it should
Carry out the displacement of catalyst, a part or whole part is replaced.This substitute mode is replaced according to design time, does not account for reality
Border service condition is replaced, and the waste of resource or denitration discharge not up to standard are caused.
Therefore there is an urgent need to a kind of catalyst performance detection method, this method being capable of Real-time and Dynamic Detection SCR denitration process
The activity of middle catalyst, to the in due course replacement provides effective foundation for catalyst.
Invention content
Goal of the invention：It is an object of the invention to be directed to problems of the prior art, a kind of dynamic detection SCR is provided
The method of catalyst activity in denitrification process, this method are capable of detecting when the work of any moment catalyst in SCR denitration overall process
Property.
Technical solution：The method of catalyst activity during a kind of dynamic detection SCR denitration of the present invention, including with
Lower step：
(1) the flue gas flow L at a certain moment denitration reactor inlet is measured1, NO in flue gasXConcentration Dn1And exit
Flue gas flow L2With NO in the flue gas of exitXConcentration Dn2；
(2) the ammonia flow L at the moment denitration reactor inlet is measuredA, ammonia concentration An1And the ammonia in exit is dense
Spend An2；
(3) the catalyst activity percentage K at the moment is calculated,
K=[L1*Dn1-L2*Dn2]/[Dn1*L1*K1*K2*K3+(An2-An4lx)*L2]；
In formula, K1For catalyst activity decay factor, K caused by oxygen content inside Benitration reactor1≤1；K2For by ammonia
Denitration efficiency impact factor caused by tolerance, K2≤1；K3Decay for the catalyst activity caused by Benitration reactor internal temperature
The factor, K3≤1；An4lxAllow the ammonia concentration of discharge for Benitration reactor exit.
Specifically, by measuring the oxygen content Y inside Benitration reactornTo determine decay of activity factor K1Value,
Work as YnWhen >=5%, K1=1；
Work as YnWhen < 5%, K1=6.67Yn+0.667。
Above-mentioned denitration efficiency impact factor K2Value determine by the following method：Assuming that catalyst activity caused by ammonia amount
Attenuation coefficient is Kn1, K2Value and Kn1It is closely related；
Kn1=(An1*LA-An4lx*L2)/(L1*Dn1-L2*Dn2), work as Kn1<When 1, K2=Kn1；When ammonia amount is more than certain value
When, that is, work as Kn1When >=1, K2=1.
Above-mentioned decay of activity factor K3Value can pass through measure Benitration reactor in temperature TnTo determine：
Work as TnWhen > T, K3=1；
Work as T*10%<Tn<When T, K3=Tn/T；
Work as T*10%>TnWhen, K3=Tn 2/T2；
Wherein, T is the optimum temperature of catalyst in out of stock reaction process.
Advantageous effect：Compared with the prior art, the advantages of the present invention are as follows the present invention is by measuring denitration reactor inlet
The dynamic activity of the catalyst in denitrification process is calculated in the real time data in place and exit, knows the efficiency of denitrification process,
To instruct staff's more catalyst changeout in time, ensures the high efficiency of denitrification process, further increase entire denitrating system
Stability；Meanwhile method of the invention introduced when calculating catalyst dynamic activity three kinds of different catalyst activities influence because
Sub- K1、K2And K3, fully consider the series of factors influenced on catalyst activity during denitration reaction, it can be more accurate
The real-time activity for effectively knowing catalyst, to ensure the effective use of catalyst.
Description of the drawings
Fig. 1 is Benitration reactor and corresponding measurement point position view used by implementing the method for the present invention, in figure,
Arrow direction indicates air-flow discrepancy direction.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with the accompanying drawings.
The method of catalyst activity, includes the following steps during a kind of dynamic detection SCR denitration of the present invention：
(1) the flue gas flow L at a certain moment denitration reactor inlet is measured1, NO in flue gasXConcentration Dn1And exit
Flue gas flow L2With NO in the flue gas of exitXConcentration Dn2；
(2) the ammonia flow L at the moment denitration reactor inlet is measuredA, ammonia concentration An1And the ammonia in exit is dense
Spend An2；
(3) the catalyst activity percentage K at the moment is calculated,
K=[L1*Dn1-L2*Dn2]/[Dn1*L1*K1*K2*K3+(An2-An4lx)*L2]；
In formula, K1、K2、K3Different factors are to the impact factor of catalyst denitration reaction, K1、K2、K3Value be respectively less than
Equal to 1；An4lxAllow the ammonia concentration of discharge for Benitration reactor exit.
Wherein, K1Characterization catalyst activity decay factor caused by oxygen content inside Benitration reactor, can pass through measurement
Oxygen content Y inside Benitration reactornTo determine decay of activity factor K1Value：Work as YnWhen >=5%, K1=1；Work as YnWhen < 5%,
K1=6.67Yn+0.667；
K2For the denitration efficiency impact factor caused by ammonia amount, it is assumed that catalyst activity attenuation coefficient caused by ammonia amount
For Kn1, K2Value can pass through Kn1To determine：
Kn1=(An1*LA-An4lx*L2)/(L1*Dn1-L2*Dn2), work as Kn1<When 1, K2=Kn1；When ammonia amount is more than certain value
When, that is, work as Kn1When >=1, K2=1.
K3It, can be by measuring Benitration reactor for the catalyst activity decay factor caused by Benitration reactor internal temperature
Interior temperature TnTo determine：
Work as TnWhen > T, K3=1；
Work as T*10%<Tn<When T, K3=Tn/T；
Work as T*10%>TnWhen, K3=Tn 2/T2；
Wherein, T is the optimum temperature of catalyst in out of stock reaction process.
The catalyst in denitrification process is calculated by the real time data at measurement denitration reactor inlet and exit
Dynamic activity, know the efficiency of denitrification process, to instruct staff's more catalyst changeout in time, ensure the height of denitrification process
Efficiency further increases the stability of entire denitrating system；Meanwhile method of the invention is drawn when calculating catalyst dynamic activity
Enter three kinds of different catalyst activity decay factor K1、K2And K3, fully considered denitration reaction in the process to catalyst activity shadow
Loud series of factors can more accurately and efficiently know the real-time activity of catalyst, to ensure efficiently making for catalyst
With.
Embodiment
Such as Fig. 1, in the smoke inlet 2 of SCR denitration reactor 1, exhanst gas outlet 3, ammonia entrance 4 and Benitration reactor 1
Sensor is respectively set in inside, wherein the sensor at smoke inlet 2 is used to measure the flue gas flow before the processing of inlet
L1With NO in the flue gas before processingXConcentration Dn1, the sensor at exhanst gas outlet 3 is for measuring cigarette of the exit after denitration
Throughput L2, NO in flue gas after denitrationXConcentration Dn2And the ammonia concentration A in exitn2, the sensor at ammonia entrance 4
For measuring the ammonia flow L for entering Benitration reactorAWith ammonia concentration An1, the sensor inside Benitration reactor is used for
Measure the O of inside reactor2Concentration YnAnd Benitration reactor internal temperature Tn。
The sensor is connect with PLC controller respectively, and the calculating of catalyst activity percentage K is preset in PLC controller
Formula K=[L1*Dn1-L2*Dn2]/[Dn1*L1*K1*K2*K3+(An2-An4lx)*L2]；PLC controller can be anti-according to the preset time
The data of each sensor measurement of second mining collection, can also acquire real time data incessantly, then be obtained according to preset calculation formula
The real-time activity of catalyst.
SCP Benitration reactors exit allows the ammonia concentration A of discharge in the present embodimentn4lxFor 2ppm, the denitration used
The optimum activity temperature T of catalyst is 220 DEG C.
The real time data that a certain moment each sensor measures is as follows：
Oxygen content O inside Benitration reactor2Concentration YnIt is 4.0%, due to YnWhen < 5%, then K1=6.67Yn+ 0.667,
K is calculated1=0.938；
Benitration reactor internal temperature TnIt is 250 DEG C, is more than 220 DEG C of denitrating catalyst optimum activity temperature, it is known that K3=1；
Mark condition flue gas flow L at denitration reactor inlet1For 3050m3/ s, and sensor measures nitrogen oxidation herein
Object concentration Dn1For 250mg/m3；
Into the ammonia flow L of Benitration reactorAFor 420m3/ s, ammonia concentration An1For 1400ppm；
The nitrous oxides concentration D in Benitration reactor exitn2For 50mg/m3, and the gas flow L in exit2For
3360m3/ s, the ammonia concentration A in exitn2For 2.5ppm；K is calculated by formula2=0.98；
Above-mentioned each value is substituted into catalyst activity calculation formula, calculate the active K of catalyst is 84%.
Claims (4)
1. a kind of method of catalyst activity during dynamic detection SCR denitration, which is characterized in that include the following steps：
(1) the flue gas flow L at a certain moment denitration reactor inlet is measured1, NO in flue gasXConcentration Dn1And the cigarette in exit
Throughput L2With NO in the flue gas of exitXConcentration Dn2；
(2) the ammonia flow L at the moment denitration reactor inlet is measuredA, ammonia concentration An1And the ammonia concentration A in exitn2；
(3) the catalyst activity percentage K at the moment is calculated,
K=[L1*Dn1-L2*Dn2]/[Dn1*L1*K1*K2*K3+(An2-An4lx)*L2]；
In formula, K1For catalyst activity decay factor, K caused by oxygen content inside Benitration reactor1≤1；K2For by ammonia amount
Caused denitration efficiency impact factor, K2≤1；K3For the catalyst activity decay factor caused by Benitration reactor internal temperature,
K3≤1；An4lxAllow the ammonia concentration of discharge for Benitration reactor exit.
2. the method for catalyst activity during dynamic detection SCR denitration according to claim 1, which is characterized in that logical
Cross the oxygen content Y measured inside Benitration reactornTo determine decay of activity factor K1Value,
Work as YnWhen >=5%, K1=1；
Work as YnWhen < 5%, K1=6.67Yn+0.667。
3. the method for catalyst activity during dynamic detection SCR denitration according to claim 1, which is characterized in that institute
State denitration efficiency impact factor K2Value determined by following formula：
Kn1=(An1*LA-An4lx*L2)/(L1*Dn1-L2*Dn2)；
Work as Kn1When >=1, K2=1；
Work as Kn1<When 1, K2=Kn1。
4. the method for catalyst activity during dynamic detection SCR denitration according to claim 1, which is characterized in that logical
Cross temperature T in measurement Benitration reactornTo determine the decay of activity factor K3Value：
Work as TnWhen > T, K3=1；
Work as T*10%<Tn<When T, K3=Tn/T；
Work as T*10%>TnWhen, K3=Tn 2/T2；
Wherein, T is the optimum temperature of catalyst during denitration reaction.
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| CN102565274B (en) * | 2012-01-17 | 2014-07-30 | 广东电网公司电力科学研究院 | Modifying method for catalyst activity in power plant SCR (selective catalytic reduction) denitration system |
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