CN101940876A - Denitration method for smoke - Google Patents
Denitration method for smoke Download PDFInfo
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- CN101940876A CN101940876A CN 201010229699 CN201010229699A CN101940876A CN 101940876 A CN101940876 A CN 101940876A CN 201010229699 CN201010229699 CN 201010229699 CN 201010229699 A CN201010229699 A CN 201010229699A CN 101940876 A CN101940876 A CN 101940876A
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- reaction product
- heat exchanger
- catalytic reduction
- flue gas
- denitration reaction
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000779 smoke Substances 0.000 title claims abstract 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 93
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 163
- 239000003546 flue gas Substances 0.000 claims description 163
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 98
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000001133 acceleration Effects 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 229910021529 ammonia Inorganic materials 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a denitration method for smoke. The method comprises the following steps of: contacting the smoke with a denitrifying agent under a selective non-catalytic reducing condition of the smoke to obtain a reaction product of non-catalytic reducing denitration, wherein the molar ratio of the nitrogen in the denitrifying agent to the nitrogen in the smoke is 0.5-2:1; injecting disturbance medium into the reaction product of non-catalytic reducing denitration to obtain a mixture of the reaction product of non-catalytic reducing denitration and the disturbance medium; reducing the temperature of the reaction product of non-catalytic reducing denitration or the mixture of the reaction product of non-catalytic reducing denitration and the disturbance medium; and contacting the mixture of the reaction product of non-catalytic reducing denitration and the disturbance medium with a catalyst under a selective catalytic reducing condition of the smoke. The denitration method for smoke according to the invention can effectively avoid local failure acceleration of a catalyst bed and/or local over escape of the denitrifying agent caused by local over high concentration of the denitrifying agent in the catalyst bed, and the denitration efficiency can reach over 75 percent.
Description
Technical field
The present invention relates to a kind of denitration method for flue gas.
Background technology
Flue gas is one of main emission of steam power plant, by the combustible generation of burning in burner (being boiler).Owing to contain a large amount of nitrogen oxide NO usually in the flue gas
x(as NO) if these nitrogen oxide directly are discharged in the atmosphere, can cause the very strong acid rain of corrosivity, so flue gas must be handled through denitrogenation (being denitration) before discharging.
At present, the gas denitrifying technology of utilization comparative maturity mainly contains two kinds: SCR (SCR) technology and SNCR denitration (SNCR) technology.The chemical principle of SCR and SNCR denitrating technique all is the same, all is denitrfying agent (urea or ammonia) is contacted with flue gas, makes the NO in denitrfying agent and the flue gas
xCarry out the selective reduction reaction and generate nitrogen (N
2) and steam (H
2O).SNCR technology generally is to carry out in the combustion zone (800-1250 ℃) in the burner hearth of boiler.SCR technology then is that beds is set in flue, under 280-420 ℃ temperature, carries out the catalytic selectivity reduction reaction of flue gas under the condition that catalyst exists.
SNCR and SCR cut both ways.The advantage of SNCR is not need expensive beds, and shortcoming is that denitration effect is relatively poor, and the denitration rate generally is no more than 40%.The shortcoming of SCR then is need to use expensive catalyst bed, and needs enough spaces beds is set, and advantage then is that denitration effect is good than SNCR, and the denitration rate is generally about 60%.
Though can improve the denitration rate of SCR a little by the thickness of further raising beds,, can cause cost significantly to improve because catalyst is relatively more expensive.
For this reason, prior art generally adopts the method for the quantity delivered that increases denitrfying agent, attempts to reduce nitrogen oxide NO in the flue gas after SCR handles with this
xContent.Yet, in fact, adopt the mode of above-mentioned increase denitrfying agent quantity delivered, not only can not reduce the nitrogen oxide NO in the flue gas after SCR handles
xContent, the amount of ammonia has increased in the flue gas after also feasible on the contrary the processing, and the life-span of beds has also reduced.
Summary of the invention
The objective of the invention is to overcome SNCR and the low problem of SCR denitration efficiency that the denitration method for flue gas of prior art exists.
The present inventor finds in practice, cause local beds to lose efficacy to quicken and/or main cause that local denitrfying agent escape amount exceeds standard is the skewness that enters denitrfying agent in the mixture of the flue gas of beds and denitrfying agent, cause in the beds local denitrfying agent concentration excessive, thereby the inefficacy of accelerator activator and/or local denitrfying agent escape amount exceed standard.
The present inventor further finds in practice, cause that denitrfying agent main cause pockety is in the mixture of flue gas and denitrfying agent: the volume of back-end ductwork is bigger, be subjected to the restriction of this body structure of boiler and position simultaneously, denitrfying agent to send into the position very limited, thereby make that the denitrfying agent that enters back-end ductwork is all inhomogeneous usually in the distribution of back-end ductwork.
The present inventor also finds, SNCR and SCR coupling are carried out the denitration processing to flue gas, can improve denitration efficiency on the one hand, can reduce the cost of investment of equipment on the other hand.
But, also there are some problems in SNCR and SCR coupling, for example: SNCR carries out under 800-1250 ℃ temperature usually, SCR carries out under 280-420 ℃ temperature usually, although can be by prolonging flue length, make the temperature of mixture of the flue gas enter beds and denitrfying agent satisfy the temperature requirement of SCR, but certainly will make that like this flue is more huge, improved the initial investment cost of denitrating flue gas equipment on the one hand, also increased the space of denitrating flue gas hold facility on the other hand, in the applied environment of some limited space, be difficult to realize SNCR and SCR are united use.
Therefore, how under the condition that does not increase equipment occupation space, realizing the coupling of SCR and SNCR, is the technical problem that needs to be resolved hurrily.
The invention provides a kind of denitration method for flue gas, this method comprises: under flue gas SNCR condition, flue gas is contacted with denitrfying agent, the nitrogen in the described denitrfying agent and the ammonia nitrogen mol ratio of the nitrogen in the flue gas are 0.5-2: 1, obtain non-catalytic reduction denitration reaction product, in non-catalytic reduction denitration reaction product, inject the disturbance medium, obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium, the temperature of the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is reduced, and under flue gas SCR condition, the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with catalyst.
According to denitration method for flue gas of the present invention, by at the mixture of flue gas and denitrfying agent with before catalyst contacts, in the mixture of flue gas and denitrfying agent, inject the disturbance medium, flue gas and denitrfying agent are mixed, thereby the local beds that prevents to cause owing to local denitrfying agent concentration in the beds is excessive lost efficacy and quickened and/or problem that local denitrfying agent escape amount exceeds standard.
According to denitration method for flue gas of the present invention, before entering beds by mixture at flue gas and denitrfying agent, reduce the temperature of flue gas and denitrfying agent and mixture, thereby on the one hand under the condition that does not increase the denitrating flue gas equipment occupation space, make the temperature of mixture of the flue gas that enters beds and denitrfying agent satisfy the requirement of SCR; Can also make full use of the heat in the flue gas on the other hand.
According to denitration method for flue gas of the present invention, denitration efficiency can be higher than 75%.
Description of drawings
Fig. 1 is the structural representation according to a kind of embodiment of the heat exchanger in the denitration method for flue gas of the present invention;
Fig. 2 is the structural representation according to a kind of embodiment of heat exchanger fin of the heat exchanger in the denitration method for flue gas of the present invention;
Fig. 3 is the structural representation according to the another kind of embodiment of the heat exchanger fin of the heat exchanger in the denitration method for flue gas of the present invention;
Fig. 4 is the structural representation of the used denitrating flue gas equipment of a kind of embodiment of denitration method for flue gas provided by the invention;
Fig. 5 is the schematic diagram of a kind of embodiment of the disturbance device in the denitration method for flue gas of the present invention;
Fig. 6 for show according to the port of disturbance device in the denitration method for flue gas of the present invention towards schematic diagram.
The specific embodiment
The invention provides a kind of denitration method for flue gas, this method comprises: under flue gas SNCR condition, flue gas is contacted with denitrfying agent, the nitrogen in the described denitrfying agent and the ammonia nitrogen mol ratio of the nitrogen in the flue gas are 0.5-2: 1, obtain non-catalytic reduction denitration reaction product, in non-catalytic reduction denitration reaction product, inject the disturbance medium, obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium, the temperature of the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is reduced, and under flue gas SCR condition, the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with catalyst.
Because among the present invention, only in non-catalytic reduction denitration reaction product, inject the disturbance medium, and do not add denitrfying agent especially, therefore, the amount of the denitrfying agent that contacts with flue gas should be enough to satisfy the requirement of reaction of flue gas SNCR and follow-up flue gas selective catalytic reduction reaction, in addition, in order to make the ammonia content compliance with environmental protection requirements of the flue gas after the denitration, flue gas and denitrfying agent are 0.5-2 with the ammonia nitrogen mol ratio of the nitrogen in the nitrogen in the denitrfying agent and the flue gas: 1 ratio contacts, and flue gas and denitrfying agent are 0.8-1.5 with the ammonia nitrogen mol ratio (hereinafter to be referred as the ammonia nitrogen mol ratio) of the nitrogen in the nitrogen in the denitrfying agent and the flue gas under the preferable case: 1 ratio contacts.Among the present invention, described ammonia nitrogen mol ratio is in the nitrogen element, refers to nitrogen in the denitrfying agent and the NO in the flue gas
xThe mol ratio of the nitrogen in (in NO).
Described denitrfying agent can be a various denitrfying agent known in the art.For example, described denitrfying agent can be for producing the material of ammonia after ammonia or the various heating, as urea.Above-mentioned denitrfying agent preferably uses with the form of its aqueous solution, and the concentration of described solution has been conventionally known to one of skill in the art, the various concentration that can reach for denitrfying agent.In order to reduce the consumption of denitrfying agent, preferred described denitrfying agent uses with the form of its saturated solution.
The condition of described flue gas and described denitrfying agent generation SNCR reaction comprises: temperature can be 800-1300 ℃, is preferably 800-1100 ℃, and the time that contacts under this temperature can be 0.1-2 second, is preferably 0.5-1 second.
Thereby said temperature can utilize the temperature of flue gas itself to realize by the position of selecting the denitrfying agent feedway, thereby need not extra heat supply or cooling.
According to denitration method for flue gas of the present invention, this method comprises injects the disturbance medium in non-catalytic reduction denitration reaction product, obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium.
Described disturbance medium can be various can be by the medium of carrier pipe ejection, having a negative impact only otherwise to the denitration reaction between flue gas and the denitrfying agent gets final product.
In order to guarantee that contacting preceding denitrfying agent and flue gas with catalyst mixes, prevent the generation of acceleration and the escaping of ammonia phenomenon because the excessive or too small local beds that causes of denitrfying agent local concentration lost efficacy in the prior art, alleviate damage simultaneously to flue, the pressure of described disturbance medium can be the 0.3-5 MPa, be preferably the 1-2 MPa, further be preferably the 1.4-1.6 MPa; The volume flow ratio of described disturbance medium and described flue gas can be 0.001-0.1: 1, be preferably 0.004-0.04: 1; The velocity ratio of described disturbance medium and described flue gas can be 10-250: 1, be preferably 10-230: and 1,10-50 more preferably: 1, further be preferably 20-30: 1; The disturbance medium injects in the mixture of non-catalytic reduction denitration reaction product and disturbance medium and 0.1 second before catalyst contacts at least, more preferably injects second with 0.5-5 before catalyst contacts at the mixture of non-catalytic reduction denitration reaction product and disturbance medium.By the cooperation of above-mentioned condition, can guarantee flue gas and denitrfying agent are mixed, thereby thoroughly prevent the generation of acceleration and the escaping of ammonia phenomenon because the excessive or too small local beds that causes of denitrfying agent local concentration lost efficacy in the prior art.
According to one embodiment of the present invention, described disturbance medium be not with the inert media of flue gas and denitrfying agent reaction, determine according to field condition and cost accounting, one or more in the group 0 element in steam, air, nitrogen and the periodic table of elements preferably, thereby can not introduce new impurity to flue gas, make that the flue gas after the denitration can directly discharge because of disturbance.
According to another embodiment of the invention, described disturbance medium is flue gas or above-mentioned non-catalytic reduction denitration reaction product.Described flue gas as the disturbance medium can be the flue gas that passes through the denitration processing or handle without denitration.When using the flue gas handled without denitration as the disturbance medium, need not the extraneous disturbance medium of supplying with on the one hand, can also make the flue gas of handling without denitration after playing perturbation action, also can obtain denitration effect on the other hand.And when using the mixture of denitrfying agent and flue gas, the mixture that particularly uses ammonia nitrogen mol ratio denitrfying agent consistent with ammonia nitrogen mol ratio in the non-catalytic reduction denitration reaction product and flue gas is during as the disturbance medium, and the feeding of disturbance medium also can not cause the significantly reduction of denitrfying agent concentration in the non-catalytic reduction denitration reaction product.Therefore, the preferred described disturbance medium of the present invention is without the flue gas of denitration processing or the mixture of denitrfying agent and flue gas, especially the mixture that preferred described disturbance medium is denitrfying agent and flue gas, the denitrfying agent that more preferred ammonia nitrogen mol ratio is consistent with ammonia nitrogen mol ratio in the non-catalytic reduction denitration reaction product and the mixture of flue gas.
According to denitration method for flue gas of the present invention, this method comprises that also the temperature with the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium reduces.
Among the present invention, the temperature of the mixture of reduction non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium can make full use of the heat in the flue gas on the one hand, can control the temperature of the mixture of the non-catalytic reduction denitration reaction product that enters catalyst and disturbance medium on the other hand, thereby make the temperature of mixture of non-catalytic reduction denitration reaction product and disturbance medium satisfy the requirement of flue gas SCR condition.Owing to make entering before the beds through the flue gas of flue gas non-selective catalytic reduction, the method according to this invention also comprises injects the disturbance medium in non-catalytic reduction denitration reaction product, reduce for fear of the temperature that causes owing to injection disturbance medium, make the temperature of mixture of non-catalytic reduction denitration reaction product and disturbance medium be difficult to satisfy the requirement of SCR, the method according to this invention preferably reduces the temperature of the mixture of non-catalytic reduction denitration reaction product and disturbance medium, that is, the present invention is preferably after injecting the disturbance medium, carry out heat exchange before entering beds.
The present invention is not particularly limited the method for temperature of the mixture of reduction non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium, can adopt the method for well known to a person skilled in the art to reduce the temperature of the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium.Preferably, the method that the temperature of non-catalytic reduction denitration reaction product or the non-catalytic reduction denitration reaction product and the mixture of disturbance medium is reduced comprises: the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is contacted with heat exchanger, and the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium and contacting of heat exchanger make that the temperature of mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is 280-420 ℃.More preferably, the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with heat exchanger, and the mixture of non-catalytic reduction denitration reaction product and disturbance medium and contacting of heat exchanger make that the temperature of mixture of non-catalytic reduction denitration reaction product and disturbance medium is 280-420 ℃.
Described heat exchanger can be this area various heat exchanger commonly used.The angle that takes up room and further improve heat exchange efficiency from further reduction flue, the present invention preferably adopts the heat exchanger with heat exchanger tube and a plurality of heat exchanger fins, wherein, described heat exchanger tube passes described heat exchanger fin, and the outer wall of heat exchanger tube closely contacts with heat exchanger fin, the heat transferring medium that is used for heat-obtaining is housed in the heat exchanger tube, and described heat transferring medium for example can be a demineralized water.As long as the temperature of heat transferring medium is lower than the temperature of the mixture of non-catalytic reduction denitration product or non-catalytic reduction denitration product and disturbance medium, for example can be 40-200 ℃.
Shown in Figure 1 is heat exchanger preferred embodiment a kind of with heat exchanger tube and a plurality of heat exchanger fins.As shown in Figure 1, described a plurality of heat exchanger fins 6 are arranged in parallel, and more than 7 past ground return of described heat exchanger tube passes a plurality of heat exchanger fins 6 that are arranged in parallel successively, forms the array of the heat exchanger tube 7 of parallel multirow and multiple row.In another preferred embodiment, a plurality of heat exchanger fins 6 are arranged in parallel, and described heat exchanger tube 7 is a plurality of, and a plurality of heat exchanger tubes 7 pass a plurality of heat exchanger fins that are arranged in parallel 6 successively, form parallel multirow and parallel multiple row heat exchanger tube array.Shown in Figure 2 is the preferred embodiment a kind of of described heat exchanger fin 6.As shown in Figure 2, be formed with the array of the pore that the size with described heat exchanger tube 7 adapts on the described heat exchanger fin 6.As shown in Figure 3, a kind of more preferred embodiment in, each heat exchanger fin 6 comprises a plurality of plate bodys, this plate body have in groove and adjacent two plate bodys groove toward each other, the space that the shape of formation and heat exchanger tube 7 adapts, described heat exchanger tube 7 passes this space and closely contacts with heat exchanger fin 6.
Among the present invention, the size and the quantity of the heat exchanger fin 6 in the described heat exchanger can in very large range change, and can carry out suitable selection according to the heat exchange efficiency of expection.Under the preferable case, the gross thickness of a plurality of heat exchanger fins that are arranged in parallel 6 can be the 10-20% of single file or single-row heat exchanger tube 7 length, under the preferred situation, the distance of two adjacent heat exchanger fins 6 can be 1-5 centimetre in a plurality of heat exchanger fins that are arranged in parallel 6, and the thickness of each heat exchanger fin 6 can be 0.5-5 centimetre in a plurality of heat exchanger fins that are arranged in parallel 6.Under the preferable case, the total sectional area that passes the heat exchanger tube 7 of each described heat exchanger fin 6 can account for the 10-50% of these heat exchanger fin 5 single face areas.There is no particular limitation for the size of described heat exchanger tube 7, can select the heat exchanger tube size of various routines for use, and for example, the sectional area of described heat exchanger tube 7 can be the 10-100 square centimeter.
In addition, in described heat exchanger, the density that described heat exchanger tube 7 is arranged can in very large range change, and under the preferable case, two adjacent in parallel multirow or the heat exchanger tube of multiple row 7 distances capable or two row heat exchanger tubes 7 can be 5-25 centimetre.
The mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is contacted with heat exchanger, thus with the temperature of the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium be controlled to be 280-420 ℃ can be by selecting heat exchanger type and the kind and the temperature of the heat transferring medium in the heat exchanger realize.
Denitration method for flue gas according to the present invention is included under the flue gas SCR condition, and the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with catalyst.
Because the present invention mixes flue gas and denitrfying agent by inject the disturbance medium in non-catalytic reduction denitration reaction product, and the temperature that reduces the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium makes the temperature of the mixture of non-catalytic reduction denitration reaction product and disturbance medium satisfy the requirement of flue gas selective catalytic reduction reaction, therefore the present invention is not particularly limited for the condition of flue gas SCR, can adopt this area flue gas selective catalytic reduction reaction commonly used.Particularly, the selective-catalytic-reduction denitrified condition of described flue gas comprises: temperature can be 280-420 ℃, is preferably 300-400 ℃; The volume space velocity of flue gas can be 200-20000 hour
-1, be preferably 1000-10000 hour
-1When described disturbance medium is aforesaid flue gas or non-catalytic reduction denitration reaction product, herein in nitrogen in the denitrfying agent and the flue gas in the NO of NO
xIn the corresponding denitrfying agent and the NO that comprises in the disturbance medium of mol ratio (ammonia nitrogen mol ratio) of nitrogen
x
Described catalyst can be various can catalytic denitration agent and nitrogen oxide NO
xReaction makes nitrogen oxide NO
xBe converted into the catalyst of nitrogen, be preferably metal oxide catalyst.
For example, described metal oxide can be V
2O
5, Fe
2O
3, CuO, Cr
2O
3, Co
3O
4, NiO, CeO
2, La
2O
3, Pr
6O
11, Nd
2O
3, Gd
2O
3, Yb
2O
3In one or more, preferred V
2O
5Further preferred described catalyst is to be dispersed in TiO
2Upward, with V
2O
5Be main active component, WO
3Or MoO
3Be the vanadium titanium system of co-catalyst, i.e. V
2O
5-WO
3/ TiO
2Or V
2O
5-MoO
3/ TiO
2
Because the existence of a large amount of flying dusts in the SCR reaction is for preventing to stop up, reduce the pressure loss, increase mechanical strength, preferably with above-mentioned V
2O
5-WO
3/ TiO
2Or V
2O
5-MoO
3/ TiO
2Catalyst is fixed on the corrosion resistant plate surface or makes the ceramic honey comb shape, forms the version of stainless steel corrugated plate dst and ceramic honey comb.Above-mentioned catalyst can be commercially available, and for example can change into available from Japanese catalyst, the Cormetech company of Hitachi, Ltd, Germany refined robust and sturdy grand company and the U.S..
Among the present invention, described flue gas can be the flue gas that various amount of nitrogen oxides need reduce, and described boiler can be power plant's boiler, also can be to smelt to use boiler.
Can in various denitrating flue gas equipment, carry out according to denitration method for flue gas of the present invention.Shown in Figure 4 is the structural representation of the used denitrating flue gas equipment of a kind of embodiment of denitration method for flue gas provided by the invention.
As shown in Figure 4, this denitrating flue gas equipment comprises flue 1 and is successively set on denitrfying agent feedway 2 in this flue 1 along the flow of flue gas direction, disturbance device 3, heat exchanger 4 and beds 5, described flue 1 comprises the first vertical section a, the second vertical section c and horizontal segment b, the two ends of described horizontal segment b are communicated with the top of the first vertical section a and the second vertical section c respectively, described denitrfying agent feedway 2 is positioned at the first vertical section a, described heat exchanger 4 and beds 5 are positioned at the second vertical section c, described disturbance device 3 is positioned at the horizontal segment b (as shown in Figure 4) or the first vertical section a (not shown), the position of described denitrfying agent feedway 2 makes described flue gas to carry out the reaction of flue gas SNCR with denitrfying agent, particularly, the distance A of the bottom of described denitrfying agent feedway 2 to first vertical section a and the top of the described first vertical section a can be 10-25 to the ratio apart from B of bottom: 30, be preferably 15-23: 30.Distance between the upper surface of the bottom of described heat exchanger 4 and described beds 5 can be 1-1.5 rice, be preferably 1.1-1.3 rice, thereby the temperature of the mixture of non-catalytic reduction denitration reaction product after can guaranteeing to contact with described heat exchanger 4 and disturbance medium satisfies the requirement of flue gas selective catalytic reduction reaction.
By denitrfying agent feedway 2 denitrfying agent is supplied in the flue 1, in flue 1, mixes, and carry out the reaction of flue gas SNCR, obtain non-catalytic reduction denitration reaction product with flue gas; Then, in flue 1, inject the disturbance medium, denitrfying agent and flue gas in the non-catalytic reduction denitration reaction product are mixed, obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium by disturbance device 3; Thereby the mixture of non-catalytic reduction denitration reaction product that obtains and disturbance medium contacts with heat exchanger 4 and reduces temperature, and then enters beds 5, contacts with catalyst, carries out the selective catalytic reduction reaction of flue gas, obtains the flue gas after the denitration.
Under the preferable case, as shown in Figure 5, described disturbance device 3 is a tube, and this tube passes the wall of flue 1, and an end port is arranged in flue 1.Further under the preferable case, in order better to obtain the disturbance effect, the angle α towards Y and flow of flue gas direction X that tube is arranged in the port of flue 1 is 70-90 ° of angle (as shown in Figure 6).
For the disturbance medium is injected in the mixture of denitrfying agent and flue gas and 0.1 second before catalyst contacts at least, more preferably inject second with 0.5-5 before catalyst contacts at the mixture of denitrfying agent and flue gas, described tube in flue 1 port and the distance between the described beds 5 be described beds 5 thickness 5-10 doubly.Wherein, port and the distance described beds 5 between of described tube in flue 1 refer in the selective-catalytic-reduction denitrified course of reaction of flue gas, and the port that flue gas is arranged in flue 1 from described tube marches to the surperficial actual distance of passing by of beds 5.
Described tube can be preferably 3-10 for one or more.Further preferred described a plurality of tubes radially or circumferentially distribute along flue 4.
Take all factors into consideration the disturbance effect and to the equipment requirement of disturbance device, the cross-sectional area of the preferred described flue 1 of the present invention is 5000-50000 with the ratio of the gross area of the port that is arranged in flue 1 of described tube: 1.Further the cross-sectional area of preferred described flue 1 is 20000-30000 with the ratio of the gross area of the port that is arranged in flue 1 of described tube: 1.
According to one embodiment of the present invention, this equipment also comprises disturbance medium generator (not shown), and disturbance medium generator provides the disturbance medium for disturbance device 3.Described disturbance medium generator can be the various devices that the disturbance medium can be provided, as steel cylinder or pump.One end port of described disturbance device 3 is communicated with disturbance medium generator, and other end port then passes the wall of described flue 1 and stretches in the described flue 1.
The supply mode of described denitrfying agent feedway 2 and denitrfying agent supply mode and flue 1 and flue gas has been conventionally known to one of skill in the art, and the present invention does not repeat them here.
Adopt method of the present invention can reach more than 75% for the denitration rate of the higher flue gas of nitrogen content, for the lower flue gas of nitrogen content, then consider the denitration cost usually, actual denitration rate requires (NO to satisfy environment protection emission
xContent is no more than 100mg/Nm
3) be as the criterion.
The following examples will the present invention is further illustrated.In following examples, NO in the flue gas
xThe content online infrared flue gas analyzer that adopts Beijing Hong Chang letter Science and Technology Ltd. to sell, product type is Gasboard-3000.
Embodiment 1
This embodiment is used to illustrate denitration method for flue gas provided by the invention.
Adopt denitrating flue gas equipment shown in Figure 4 to implement denitrating flue gas, this denitrating flue gas equipment comprises flue 1 and is successively set on denitrfying agent feedway 2, disturbance device 3, heat exchanger 4 and beds 5 in the flue 1, wherein flue 1 is that 60 millimeters 20G carbon steel pipe surrounds by diameter, the cross section of flue 1 is 10 meters * 6 meters a rectangle, dress station boiler demineralized water in the 20G carbon steel pipe.Described flue 1 has the first vertical section a, horizontal segment b and the second vertical section c, the two ends of described horizontal segment b respectively with being communicated with of the top of the first vertical section a and the second vertical section c, the height of the described first vertical section a is 30 meters, and the width of horizontal segment is 8 meters, and the height of second vertical section is 22 meters.The ratio apart from B to the bottom is 15: 30 to described denitrfying agent feedway 2 to the top of the distance A of the bottom of the described first vertical section a and the described first vertical section a.Described denitrfying agent feedway 2 is 7 playpipes, and an end of playpipe stretches in the flue, and the other end is communicated with denitrfying agent source (concentration is the aqueous solution of urea of 39 weight %).Disturbance device 3 is positioned at horizontal segment b, comprise that 5 diameters are 50 millimeters tube, 5 tubes circumferentially are evenly arranged into a row along flue 1, and an end of described tube is connected with the vapour source of 1.5MPa, the other end stretches in the flue 1, and the Way out of tube is vertical with flue gas flow direction.The thickness of beds 5 is 1.8 meters, beds 5 by refined robust and sturdy grand ceramic product trade (Shanghai) Co., Ltd. sell (manufacturer: Johnson Matthey Catalysts (Germany)) the board-like catalyst of the titania-based SCR of GmbH forms.
Heat exchanger 4 is positioned at the second vertical section c, be H type fin economizer available from Beijing uncle million maple changes in temperature equipment Co., Ltds, heat exchanger tube array with 35 row * 35 row, the distance of two adjacent row heat exchanger tubes is 10 centimetres in the parallel multirow heat exchanger tube, the distance of two adjacent row heat exchanger tubes is 15 centimetres in the parallel multirow heat exchanger tube, and the cross-sectional area of heat exchanger tube is 80 square centimeters; Have 280 heat exchanger fins, the gross thickness of heat exchanger fin is 15% of single file or a single-row heat exchanger tube length, and the distance between two adjacent heat exchanger fins is 2.5 centimetres, and the thickness of each heat exchanger fin is 5 millimeters; The total sectional area that passes the heat exchanger tube of each described heat exchanger fin accounts for 40% of this heat exchanger fin single face area.Temperature be housed be 200 ℃ station boiler demineralized water steam in the heat exchanger 6.8 meters of the distances at the top of the upper surface of beds 5 and the second vertical section c, with the distance of the bottom of heat exchanger 4 be 1.5 meters.
Is that the aqueous solution of urea of 39 weight % is sent in the flue by denitrfying agent feedway 2 with concentration, with temperature be 1100 ℃, flow be 70 ten thousand steres/hour the flue gas from boiler of power plant (content of nitrogen oxide is 350mg/Nm
3) mix, the ammonia nitrogen mol ratio that makes the nitrogen oxide in aqueous solution of urea and the flue gas is 1.1: 1, the time that flue gas contacts with this aqueous solution of urea was 1.1 seconds, obtained non-catalytic reduction denitration reaction product.To send in the flue with 4.19 tons/hour amount as the steam of disturbance medium by above-mentioned tube (being that 350 ℃ steam jar of 1.5 MPas is connected with pressure separately), obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium as disturbance device 3.Wherein, the volume of steam per ton is 2871 cubic metres, therefore, can learn that by calculating the volume flow ratio of disturbance medium and described flue gas is 0.017: 1, velocity ratio is 105: 1, flue gas is 6482 hours-1 by the volume space velocity of beds 5, and the disturbance medium injected in non-catalytic reduction denitration reaction product and 4.32 seconds before catalyst contacts.Record NO in the flue gas after the denitration
xContent be 48mg/Nm
3, NO
xConversion ratio be 86.3 weight %.
Comparative Examples 1
Method according to embodiment 1 is carried out denitration to flue gas, and different is, does not send into steam in the mixture of flue gas and denitrfying agent, records NO in the flue gas after the denitration
xContent be 110mg/Nm
3, apparently higher than embodiment 1; NO
xConversion ratio be 68.6 weight %, be starkly lower than embodiment 1.
Comparative Examples 2
Method according to embodiment 1 is carried out denitration to flue gas, different is, the mixture of described non-catalytic reduction denitration reaction product and disturbance medium is without heat exchange, the temperature of the mixture of the non-catalytic reduction denitration reaction product of beds porch and disturbance medium is 650 ℃ as a result, can't satisfy the requirement of flue gas selective catalytic reduction reaction.
This embodiment is used to illustrate denitration method for flue gas provided by the invention.
Method according to embodiment 1 is carried out denitration to flue gas, different is, the ammonia nitrogen mol ratio of the nitrogen oxide in aqueous solution of urea and the flue gas is 0.8: 1,350 ℃ steam is sent in the mixture of flue gas and denitrfying agent with 5 tons/hour amount, wherein, the volume flow ratio of disturbance medium and described flue gas is 0.02: 1, and velocity ratio is 125: 1.Record NO in the flue gas after the denitration
xContent be 51mg/Nm
3, NO
xConversion ratio be 85.4 weight %.
This embodiment is used to illustrate denitration method for flue gas provided by the invention.
Method according to embodiment 1 is carried out denitration to flue gas, and different is that the content of the nitrogen oxide of flue gas is 550mg/Nm
3Denitrfying agent is that concentration is the ammonia spirit of 25 weight %, the ammonia nitrogen mol ratio of the nitrogen oxide in ammonia spirit and the flue gas is 1.5: 1,350 ℃ steam is sent in the mixture of flue gas and denitrfying agent with 7 tons/hour amount, wherein, the volume flow ratio of disturbance medium and described flue gas is 0.029: 1, and velocity ratio is 175.5: 1, and the flow of ammonia spirit makes the NO in denitrfying agent and the flue gas
xThe ammonia nitrogen mol ratio be 1.2: 1.Record NO in the flue gas after the denitration
xContent be 45mg/Nm
3, NO
xConversion ratio be 91.8 weight %.
Embodiment 4
This embodiment is used to illustrate denitration method for flue gas provided by the invention.
Method according to embodiment 1 is carried out denitration to flue gas, and different is, 350 ℃ steam is sent into 1 ton/hour amount in the mixture of flue gas and denitrfying agent, and wherein, the volume flow ratio of disturbance medium and described flue gas is 0.004: 1, and velocity ratio is 25.1: 1.Record after the denitration NO in the flue gas
xContent be 74.4mg/Nm
3, NO
xConversion ratio be 78.7 weight %.
Claims (12)
1. denitration method for flue gas, it is characterized in that, this method comprises: under flue gas SNCR condition, flue gas is contacted with denitrfying agent, the nitrogen in the described denitrfying agent and the ammonia nitrogen mol ratio of the nitrogen in the flue gas are 0.5-2: 1, obtain non-catalytic reduction denitration reaction product, in non-catalytic reduction denitration reaction product, inject the disturbance medium, obtain the mixture of non-catalytic reduction denitration reaction product and disturbance medium, the temperature of the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is reduced, and under flue gas SCR condition, the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with catalyst.
2. method according to claim 1, wherein, the pressure of described disturbance medium is the 0.3-5 MPa, the volume flow ratio of described disturbance medium and described non-catalytic reduction denitration reaction product is 0.001-0.1: 1, velocity ratio is 10-250: 1, and the disturbance medium injects in the mixture of non-catalytic reduction denitration reaction product and disturbance medium and 0.1 second before catalyst contacts at least.
3. method according to claim 2, wherein, the pressure of described disturbance medium is the 1-2 MPa, the volume flow ratio of described disturbance medium and described non-catalytic reduction denitration reaction product is 0.004-0.04: 1, velocity ratio is 20-230: 1, and the disturbance medium injects with 0.5-5 before catalyst contacts at the mixture of non-catalytic reduction denitration reaction product and disturbance medium second.
4. according to any described method among the claim 1-3, wherein, described disturbance medium be not with the inert media of denitrfying agent and smoke reaction.
5. method according to claim 4, wherein, described disturbance medium is one or more in steam, air and the nitrogen.
6. according to any described method among the claim 1-3, wherein, described disturbance medium is flue gas or described non-catalytic reduction denitration reaction product.
7. method according to claim 1, wherein, the method that the temperature of non-catalytic reduction denitration reaction product or the non-catalytic reduction denitration reaction product and the mixture of disturbance medium is reduced comprises: the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is contacted with heat exchanger, and the mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium and contacting of heat exchanger make that the temperature of mixture of non-catalytic reduction denitration reaction product or non-catalytic reduction denitration reaction product and disturbance medium is 280-420 ℃.
8. method according to claim 7, wherein, the mixture of non-catalytic reduction denitration reaction product and disturbance medium is contacted with heat exchanger, and the mixture of non-catalytic reduction denitration reaction product and disturbance medium and contacting of heat exchanger make that the temperature of mixture of non-catalytic reduction denitration reaction product and disturbance medium is 280-420 ℃.
9. according to claim 7 or 8 described methods, wherein, described heat exchanger comprises heat exchanger tube, a plurality of heat exchanger fin and is contained in the interior heat transferring medium of heat exchanger tube that described heat exchanger tube passes described heat exchanger fin, and the outer wall of heat exchanger tube closely contacts with heat exchanger fin.
10. method according to claim 9, wherein, described a plurality of heat exchanger fins are arranged in parallel, and described heat exchanger tube repeatedly passes a plurality of heat exchanger fins that are arranged in parallel successively toward ground return, forms the parallel multirow and the heat exchanger tube array of multiple row.
11. method according to claim 10, wherein, described a plurality of heat exchanger fins are arranged in parallel, and described heat exchanger tube is a plurality of, and a plurality of heat exchanger tubes pass a plurality of heat exchanger fins that are arranged in parallel successively, form the parallel multirow and the heat exchanger tube array of multiple row.
12. method according to claim 1, wherein, described flue gas SNCR condition comprises: temperature is 800-1300 ℃, and be 0.1-2 second the time of contact of flue gas and denitrfying agent; Described flue gas SCR condition comprises: temperature is 280-420 ℃, and the volume space velocity of flue gas is 200-20000 hour-1.
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| CN114113498A (en) * | 2022-01-25 | 2022-03-01 | 光大环保技术装备（常州）有限公司 | Fluid flow velocity reverse disturbance purification test system and method for SCR denitration system |
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