CN101940878A - Method for denitrating gas fume - Google Patents
Method for denitrating gas fume Download PDFInfo
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- CN101940878A CN101940878A CN 201010229710 CN201010229710A CN101940878A CN 101940878 A CN101940878 A CN 101940878A CN 201010229710 CN201010229710 CN 201010229710 CN 201010229710 A CN201010229710 A CN 201010229710A CN 101940878 A CN101940878 A CN 101940878A
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- flue gas
- denitrfying agent
- mixture
- catalyst
- flue
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000007789 gas Substances 0.000 title abstract description 11
- 239000003517 fume Substances 0.000 title abstract 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 170
- 239000000203 mixture Substances 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 154
- 239000003546 flue gas Substances 0.000 claims description 154
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 70
- 229910021529 ammonia Inorganic materials 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000000779 smoke Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract 2
- 230000001502 supplementing effect Effects 0.000 abstract 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 24
- 239000004202 carbamide Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 241000264877 Hippospongia communis Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a method for denitrating gas fume. The method comprises the following steps of: contacting the gas fume with a denitrating agent under the condition of selective non catalyst reduction of the gas fume to obtain a first mixture; supplementing the denitrating agent and injecting a disturbing medium into the first mixture respectively to obtain a second mixture; and contacting the second mixture with a catalyst under the condition of the selective catalyst reduction of the gas fume. The method can effectively solve the problem of high NOx content in the gas fume and completely denitrates the gas fume in the true sense by supplementing the denitrating agent and disturbing the denitrating agent and the gas fume between a selective non catalyst reduction process of the gas fume and another selective catalyst reduction process of the gas fume.
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
xAs 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 before discharging through denitrogenation (being denitration).
At present, the gas denitrifying technology of utilization comparative maturity mainly contains two kinds: SCR (SCR) technology and SNCR denitration (SNCR) technology.SNCR technology generally sprays into denitrfying agent in the burner hearth of 800-1300 ℃ of boiler, 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
2And discharge and flue gas after denitrfying agent contacts O).The problem that SNCR technology exists is that the efficient of denitration is low, and the denitration efficiency of general SNCR denitration technology is below 40%.
SCR technology then is that beds is set in flue, under 280-420 ℃ of temperature, carries out the catalytic selectivity reduction reaction under the condition that catalyst exists.The denitration efficiency of SCR technology is higher relatively than SNCR, generally can reach 50-60%.
And although SCR denitration effect good than SNCR technology, as mentioned above, the denitration rate of SCR also only is below 60%, remains further to be improved.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.
Summary of the invention
The objective of the invention is provides a kind of denitration rate higher denitration method for flue gas in order to overcome the lower shortcoming of denitration rate that SNCR technology and SCR technology exist in the prior art.
In order effectively to improve the denitration rate, the present inventor attempts by increase the quantity delivered of denitrfying agent in the non-catalytic reduction denitration district of flue gas, and the flue afterbody after being positioned at non-catalytic reduction denitration district increases a beds, make the flue gas after the on-catalytic denitration directly carry out selective-catalytic-reduction denitrified, yet but be surprised to find that, along with the obvious increase of on-catalytic denitration district denitrfying agent quantity delivered in the flue, the nitrogen oxide NO in the flue gas
xAmount not only do not reduce, rise to some extent in above-mentioned scope the time than denitrfying agent on the contrary, this may be because ammonia has been oxidized to NO
xIn addition, the present inventor also finds, because the volume of back-end ductwork is bigger, is subjected to the restriction of this body structure of boiler and position simultaneously, denitrfying agent to send into the position very limited, thereby it is all inhomogeneous usually in the distribution of back-end ductwork to enter the denitrfying agent of back-end ductwork.And the uniformity of denitrfying agent is very big for the denitration efficiency influence of SCR system.If enter the ammonia skewness of SCR catalyst, will speed up the inefficacy of catalyst for the big position of ammonia concentration, the position little for ammonia concentration do not reach the denitration efficiency of design again, and the ammonia skewness must cause local amount of ammonia slip to exceed standard.Therefore, making ammonia also is to improve one of the key of SCR system denitration efficiency place in the even distribution of back-end ductwork.
In order to address the above problem, the present inventor has carried out a large amount of research, found that, by denitrfying agent being carried out supply and denitrfying agent and flue gas are carried out disturbance, can effectively solve NO in the flue gas in the SNCR course of reaction of flue gas and the selective catalytic reduction reaction process interval of flue gas
xThe content problem of higher realizes abundant denitrating flue gas truly.
The invention provides a kind of denitration method for flue gas, wherein, this method is included under the flue gas SNCR condition, flue gas is contacted with denitrfying agent, obtain first mixture, in first mixture, mend denitrfying agent respectively and inject the disturbance medium, obtain second mixture, under flue gas SCR condition, second mixture is contacted with catalyst.
According to denitration method for flue gas of the present invention, under flue gas SNCR condition, flue gas contacted with denitrfying agent belong to the SNCR process, under flue gas SCR condition, second mixture contacted with catalyst belong to the SCR process, by in the SNCR of flue gas process with the SCR process is interval mends denitrfying agent and inject the disturbance medium, the SNCR and the SCR combined denitration of flue gas have really been realized, thereby under the situation that guarantees denitration efficiency, reduced catalyst consumption, reduced cost.The present inventor thinks that the mechanism that can realize so significant effect may be by analysis: go into denitrfying agent in the SNCR of flue gas process and the interval benefit of SCR process, the denitrfying agent that benefit is gone into can play and suppress NO in the SNCR process
xThe backward reaction of reduction reaction effectively reduces NO in the flue gas that enters the SCR process area
xContent, thus catalyst consumption in the SCR process can be reduced, mend the denitrfying agent of going on the other hand and can enter the SCR reaction zone with flue gas, under the effect of catalyst, carry out denitration reaction, further improve SCR process denitration efficiency; By injecting the disturbance medium, make denitrfying agent when carrying out the SCR reaction, evenly distribute, thereby the problem of both having avoided the excessive catalyst that causes of local ammonia concentration to lose efficacy fast, also avoided the too small problem that can not realize abundant denitration of local ammonia concentration, but also avoided because the problem that the denitrfying agent skewness causes amount of ammonia slip to exceed standard.
Description of drawings
Fig. 1 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. 2 is the partial structurtes schematic diagram of disturbance device position in the used denitrating flue gas equipment of a kind of embodiment that shows denitration method for flue gas provided by the invention;
Fig. 3 is when disturbance device is tube in the used denitrating flue gas equipment of a kind of embodiment that shows denitration method for flue gas provided by the invention, and tube is arranged in the schematic diagram towards the angle α of Y and flow of flue gas direction X of the port of flue.
The specific embodiment
According to denitration method for flue gas provided by the invention, this method is included under the flue gas SNCR condition, flue gas is contacted with denitrfying agent, obtain first mixture, in first mixture, mend denitrfying agent respectively and inject the disturbance medium, obtain second mixture, under flue gas SCR condition, second mixture is contacted with catalyst.
According to method provided by the invention, wherein, the front and back of mending denitrfying agent and injection disturbance medium in first mixture respectively do not have special requirement in proper order, make flue gas and denitrfying agent mix as long as guarantee the degree of disturbance, can suitably select according to actual conditions.In the preferred case, in first mixture, mend denitrfying agent earlier, then, the disturbance medium that reinjects carries out disturbance to mending the denitrfying agent and first mixture of going into, like this, by mending the disturbance medium that reinjects behind the denitrfying agent, can realize that denitrfying agent and flue gas mix more fully.
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 the second preceding mixture with catalyst mixes, prevent in the prior art because the generation of excessive or too small catalyst poisoning that causes of denitrfying agent local concentration and the escaping of ammonia phenomenon, alleviate damage simultaneously to following flue, under the preferable case, the pressure of described disturbance medium is the 0.3-5 MPa, more preferably the 1-2 MPa further is preferably the 1.4-1.6 MPa; The volume flow ratio of described disturbance medium and described first mixture is 0.001-0.1: 1, and 0.004-0.04 more preferably: 1; Velocity ratio is 10-250: 1, and 10-230 more preferably: 1,10-50 more preferably: 1, further be preferably 20-30: 1; The disturbance medium injects in the mixture of denitrfying agent and flue gas and 0.1 second before catalyst contacts at least, is more preferably injecting second with 0.5-5 before catalyst contacts at the mixture of denitrfying agent and flue gas.By cooperating of above-mentioned pressure and flow and flow velocity, can guarantee second mixture with fully mix before catalyst contacts, thereby thoroughly prevent in the prior art because the generation of excessive or too small catalyst poisoning that causes of denitrfying agent local concentration and the escaping of ammonia phenomenon.
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 because of disturbance, the flue gas after the denitration can directly discharge.
According to another embodiment of the invention, described disturbance medium is the mixture of flue gas or denitrfying agent and flue gas.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, when particularly using described first mixture as the disturbance medium, the feeding of disturbance medium also can not cause the significantly reduction of denitrfying agent concentration in second mixture.Therefore the preferred disturbance medium of the present invention is without the flue gas of denitration processing or the mixture of denitrfying agent and flue gas, and especially preferred disturbance medium is described first mixture.
According to method provided by the invention, the material that can produce ammonia after adopting heating is as under the situation of mending the denitrfying agent of going into, as long as mend in described first mixture selective-catalytic-reduction denitrified reaction can take place when contacting with catalyst though can produce the material of ammonia after will heating, but, the present inventor finds, when the material that can produce ammonia after the described heating is mended in described first mixture, if the temperature of described first mixture can produce 300 ℃ of the high less thaies of decomposition temperature of the material of ammonia after than this heating, the material that then can produce ammonia after this heating is mended into the speed that resolves into ammonia after described first mixture slower, thereby makes the material that can produce ammonia after this heating be not fully utilized; And if the material that can produce ammonia after the described heating mend into time to time interval of contact with catalyst be during less than 4 seconds, the ammonia that then can cause producing the substance decomposition of ammonia after this heating mixes inhomogeneous with described first mixture.And, the present inventor is surprised to find that, under the situation of mending the material that can produce ammonia after the denitrfying agent of going into is heating, if the temperature of first mixture is higher at least 300 ℃ than the decomposition temperature of denitrfying agent when mending denitrfying agent, time to the time interval that contacts with catalyst of mend denitrfying agent is when being at least 4 seconds, the material that can produce ammonia after the described heating can resolve into ammonia rapidly, and evenly mix with described first mixture, and, in this case, compare as the situation of mending the denitrfying agent of going into adopting ammoniacal liquor, can improve the denitration rate greatly.Under the preferable case, in the time of after the denitrfying agent that benefit is gone into is heating, can producing the material of ammonia, the temperature of first mixture is higher at least 600 ℃ than the decomposition temperature of denitrfying agent when mending denitrfying agent, and time to the time interval that contacts with catalyst of mending denitrfying agent is 4-20 second.Under further preferable case, the temperature of non-catalytic reduction denitration reaction product is lower than the temperature that flue gas contacts with denitrfying agent under the SNCR reaction condition when mending denitrfying agent, also promptly is lower than 950 ℃.
The amount of the denitrfying agent of mend to be satisfying the requirement of SCR reaction, under the preferable case, mends denitrfying agent and makes in described second mixture in the nitrogen element NO in nitrogen and the flue gas in the denitrfying agent
xThe mol ratio (be called for short ammonia nitrogen mol ratio) of nitrogen (in NO) be 0.5-1.1: 1.
The present invention is chiefly directed to the SNCR process and the interval benefit of SCR process of flue gas and goes into denitrfying agent and inject the disturbance medium, therefore the reaction of the SNCR between flue gas and the denitrfying agent and the actual conditions of selective catalytic reduction reaction and the kind of denitrfying agent being not particularly limited, can be that SNCR reaction condition known in the art and selective catalytic reduction reaction are answered condition and denitrfying agent kind.For example, described denitrfying agent can be for can producing the material of ammonia after ammonia or the various heating, but under the preferable case, as mentioned above, mending the denitrfying agent of going into is urea liquid.In addition, the denitrfying agent that contacts with flue gas under flue gas SNCR condition can be identical or different with the denitrfying agent that benefit in first mixture is gone into, and for example can be urea or ammonia.
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.
According to method provided by the invention, wherein, 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, i.e. the preferred described catalyst of the present invention is the beds form.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..
According to denitration method for flue gas provided by the invention, wherein, the condition of flue gas SNCR denitration comprises: the temperature that flue gas contacts with denitrfying agent can be 800-1300 ℃, is preferably 800-1100 ℃; The time of contact is preferably 0.1-2 second, more preferably 0.5-1 second; In the nitrogen element, NO in nitrogen and the flue gas in the denitrfying agent
xThe mol ratio (be called for short ammonia nitrogen mol ratio) of nitrogen (in NO) can be 0.3-1.5: 1, be preferably 0.3-1.1: 1.
According to denitration method for flue gas provided by the invention, wherein, in the nitrogen element, NO in nitrogen and the flue gas in the denitrfying agent in second mixture
xThe mol ratio (be called for short ammonia nitrogen mol ratio) of nitrogen (in NO) can be 0.5-1.1: 1, be preferably 0.7-1: 1.When described disturbance medium is aforesaid flue gas or contains denitrfying agent and the mixture of flue gas during as first mixture, NO in the ammonia of denitrfying agent and the flue gas herein
xCorresponding ammonia and the NO that comprises the denitrfying agent in the disturbance medium of mol ratio (ammonia nitrogen mol ratio)
x
According to denitration method for flue gas provided by the invention, wherein, the selective-catalytic-reduction denitrified condition of flue gas comprises: the temperature that second mixture contacts with catalyst 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
-1
Among the present invention, described flue gas can be the flue gas that various amount of nitrogen oxides need reduce, and for example can be without the flue gas that comes boiler of power plant of any processing or from the flue gas of steel-making boiler.
Below in conjunction with accompanying drawing one embodiment of the present invention are described in detail.
According to one embodiment of the present invention, denitration method for flue gas provided by the invention can adopt denitrating flue gas equipment as shown in Figure 1 to realize.
As shown in Figure 1, described denitrating flue gas equipment comprises flue 1 and is successively set on denitrfying agent feedway 2 and beds 5 in this flue 1 along the flow direction of flue gas, and denitrfying agent device for supplying 3 and disturbance device 4, described denitrfying agent device for supplying 3 and disturbance device 4 are successively set in the flue 1 between denitrfying agent feedway 2 and the beds 5.Described denitrfying agent feedway 2 is used for providing in described flue 1 denitrfying agent to contact with flue gas, reacts thereby SNCR takes place; First mixture that described denitrfying agent device for supplying 3 is used for obtaining after contacting under the SNCR condition to flue gas and denitrfying agent mends denitrfying agent, and pass through disturbance device 4 and in flue 1, inject the disturbance medium, denitrfying agent and flue gas are evenly mixed under the disturbance of disturbance medium, pass through beds 5 afterwards, carry out the selective catalytic reduction reaction of flue gas, obtain the flue gas after the denitration.
The cross section of described flue 1 can be circle, ellipse, rectangle, square or various irregularly shaped, flue 1 itself can be kept straight on, it also can be bending, according to one embodiment of the present invention, described flue comprises the first vertical section a, the second vertical section c and a horizontal segment b between these two vertical sections, and the two ends of described horizontal segment b are communicated with the top of the first vertical section a, the second vertical section c separately.
According to one embodiment of the present invention, described denitrfying agent feedway 2 and denitrfying agent device for supplying 3 are positioned at the first vertical section a, and described beds 5 is positioned at the second vertical section c.Under the preferable case, denitrfying agent feedway 2 to the distance A of the bottom of these denitrfying agent feedway 2 place vertical sections, denitrfying agent feedway 2 to described denitrfying agent device for supplying 3 apart from the bottom of B, these denitrfying agent device for supplying 3 place vertical sections to preferably satisfied between the distance C at top: A: B: C=10-25: 5-15: 30, more preferably A: B: C=15-23: 5-13: 30.The position that the denitrfying agent that this moment, described denitrfying agent device for supplying 3 was supplied with enters described flue temperature of described flue when using is the zone about 800 ℃, when helping denitrfying agent and being urea, makes urea be decomposed into ammonia.Generally, when being 10 meters of 30 meters, 10 meters of width, the degree of depth with respect to the height of the first vertical section a of flue, described denitrfying agent device for supplying 3 is positioned at the position of the 23-28 rice of the described first vertical section a, and described denitrfying agent feedway 2 is positioned at the position of the 15-23 rice of the described first vertical section a.
According to another embodiment of the invention, described denitrfying agent feedway 2 is positioned at the first vertical section a, and denitrfying agent device for supplying 3 is positioned at horizontal segment b, and beds 5 is positioned at the second vertical section c.This embodiment is applicable to that the denitrfying agent of denitrfying agent device for supplying 3 supplies is the situation of ammoniacal liquor.
According to another embodiment of the invention, described denitrating flue gas equipment also comprises denitrfying agent source (not shown), for denitrfying agent feedway 2 and denitrfying agent device for supplying 3 provide denitrfying agent.Described denitrfying agent source for example can be denitrfying agent storage tank or pump.One end port of described denitrfying agent feedway 2 and denitrfying agent device for supplying 3 is communicated with the denitrfying agent source, and other end port then passes the wall of described flue 1 and stretches in the described flue 1.Denitrfying agent feedway 2 and denitrfying agent device for supplying 3 can shared denitrfying agent sources, also can be separately be communicated with different denitrfying agent source, provide denitrfying agent by different denitrfying agent sources.
In described denitrating flue gas equipment, although the various devices that can be used to provide denitrfying agent all can be made described denitrfying agent feedway 2 and described denitrfying agent device for supplying 3, but under the preferable case, described denitrfying agent feedway 2 and described denitrfying agent device for supplying 3 pipeline of respectively doing for oneself, this pipeline passes the wall of flue 1, stretch in the flue 1, stretch on the pipeline in the flue 1 and be formed with opening.Denitrfying agent enters in the flue by this opening.Described pipeline is preferably many, for example can be the 3-10 root.Further under the preferable case, described many pipelines are along the axial or circumferential array of flue 1.Under the preferred situation, described many pipelines are along the axially-aligned of flue 1 and radially evenly distributing along flue 1.Opening on every pipeline that stretches in the flue 1 can be for a plurality of, as 2-20.A plurality of openings on the preferred every pipeline that stretches in the flue 1 are along the axial distribution of described pipeline.In order to make described denitrfying agent more abundant with contacting of flue gas, the direction of described opening is opposite with the direction of flow of flue gas in the flue 1, thereby flue gas with contact in the same way from the described denitrfying agent of described denitrfying agent feedway 2 and denitrfying agent device for supplying 3 is non-, can better obtain denitration effect.In the present invention, the direction of described opening is opposite with the direction of flow of flue gas in the flue 1 to be not absolute opposite, the direction that comprises described opening down, towards the situation of level or downward-sloping 1-15 °.The cross-sectional area of described flue can be 5000-50000 with the ratio of the gross area of the opening of described denitrfying agent feedway 2: 1, be preferably 20000-30000: 1.The cross-sectional area of described flue is 5000-50000 with the ratio of the gross area of the opening of described denitrfying agent device for supplying 3: 1, be preferably 20000-30000: 1.
Preferable case, as shown in Figure 2, described disturbance device 4 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, as shown in Figure 3, 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.
Fully mixed before mending second mixture that obtains behind denitrfying agent and the injection disturbance medium in first mixture respectively enters beds 5 in order to make, under the preferable case, 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 1.
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 4.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 4 is communicated with disturbance medium generator, and other end port then passes the wall of described flue 1 and stretches in the described flue.
In described denitrating flue gas equipment, described beds 5 is the catalyst bed that is formed by catalyst, and there is no particular limitation for the thickness of described beds 5, and under the preferable case, the thickness of described beds 5 can be 1.5-2 rice.
In order to make full use of the heat in the flue gas, under the preferable case, the part that the beds of the first vertical section a, the horizontal segment b at denitrfying agent feedway 2 places of the especially described flue 1 of described flue 1 and the beds 5 places second vertical section c (is as the criterion with flue gas flow direction) more than 5 is surrounded by metal tube.Described metal tube for example can be carbon steel pipe, stainless steel tube, copper pipe, titanium pipe or various metal alloy pipes etc.
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.
This embodiment is used to illustrate described denitration method for flue gas provided by the invention.
Adopt denitrating flue gas equipment shown in Figure 1 to implement denitrating flue gas, this denitrating flue gas equipment comprises flue 1 and is successively set on denitrfying agent feedway 2, denitrfying agent device for supplying 3, disturbance device 4 and beds 5 in the flue 1, wherein flue is that 60 millimeters 20G carbon steel pipe surrounds by diameter, the cross section of flue is 10 meters * 6 meters a rectangle, dress station boiler demineralized water in the 20G carbon steel pipe.Described flue 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.Minimum range B and the described denitrfying agent device for supplying 3 of described denitrfying agent feedway 2 to the minimum range A of the bottom of the described first vertical section a, described denitrfying agent feedway 2 to described denitrfying agent device for supplying 3 is 15: 5: 30 to the ratio of the minimum range C at the top of described first vertical section 5.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 %); Described denitrfying agent device for supplying 3 is 3 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 %).The minimum range that disturbance device 4 is positioned at distance second vertical section is 6 meters, comprise that 5 diameters are 50 millimeters tube, 5 tubes circumferentially are evenly arranged into a row along flue 1, one 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, 8 meters at the top of the upper surface of beds 5 distance second vertical section, 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.
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 900 ℃, 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, the time that flue gas contacts with this aqueous solution of urea was 1.1 seconds.And to mend concentration in first mixture that produces after above-mentioned contact by denitrfying agent device for supplying 3 be the aqueous solution of urea (at this moment, the temperature of above-mentioned first mixture is 850 ℃) of 39 weight %, and making the ammonia nitrogen mol ratio in this mixture is 0.8: 1.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) again, obtain second mixture as disturbance device 4.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, and velocity ratio is 105: 1, and flue gas is 6482 hours by the volume space velocity of beds 5
-1, the disturbance medium injected in second mixture and 4.32 seconds before catalyst contacts.Record NO in the flue gas after the denitration
xContent be 45mg/Nm
3, NO
xConversion ratio be 87.1 weight %.
Comparative Examples 1
Method according to embodiment 1 is implemented denitrating flue gas, different is, the amount of sending into the aqueous solution of urea of 39 weight % in the flue 1 by denitrfying agent feedway 2 is to send into the total amount of the aqueous solution of urea in the flue 1 among the embodiment 1 by denitrfying agent feedway 2 and denitrfying agent device for supplying 3, and by denitrfying agent device for supplying 3 transport urea aqueous solution in flue 1.Record NO in the flue gas after the denitration at last
xContent be 200mg/Nm
3, NO
xConversion ratio be 42.9 weight %.
Comparative Examples 2
Method according to embodiment 1 is implemented denitrating flue gas, and different is not send into steam by disturbance device 4 in flue 1.Record NO in the flue gas after the denitration
xContent be 180mg/Nm
3, NO
xConversion ratio be 48.6 weight %.
Embodiment 2
This embodiment is used to illustrate described denitration method for flue gas provided by the invention.
Adopt the denitrating flue gas equipment enforcement denitrating flue gas identical with embodiment 1, particularly, 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 1000 ℃, flow be 77.8 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 0.3: 1, the time that flue gas contacts with this aqueous solution of urea was 1.2 seconds.And to mend concentration in first mixture that produces after above-mentioned contact by denitrfying agent device for supplying 3 be the aqueous solution of urea (at this moment, the temperature of above-mentioned first mixture is 850 ℃) of 39 weight %, and making the ammonia nitrogen mol ratio in this mixture is 1: 1.To send in the flue with 5 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) again, obtain second mixture as disturbance device 4.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 0.018: 1, velocity ratio is 113: 1, flue gas is 7204 hours-1 by the volume space velocity of beds 5, and the disturbance medium injected in the mixture of denitrfying agent and flue gas and 3.89 seconds before catalyst contacts.Record NO in the flue gas after the denitration
xContent be 50mg/Nm
3, NO
xConversion ratio be 85.7 weight %.
Embodiment 3
This embodiment is used to illustrate described denitration method for flue gas provided by the invention.
Adopt the denitrating flue gas equipment enforcement denitrating flue gas identical with embodiment 1, particularly, 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 60 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 0.8: 1, the time that flue gas contacts with this aqueous solution of urea was 0.5 second.And to mend concentration in the mixture that produces after above-mentioned contact by denitrfying agent device for supplying 3 be the aqueous solution of urea (at this moment, the temperature of first mixture that produces after the above-mentioned contact is 800 ℃) of 39 weight %, and making the ammonia nitrogen mol ratio in this mixture is 0.7: 1.To send in the mixture of above-mentioned flue gas in the flue and denitrfying agent with 7 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) again as disturbance device 4.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 0.033: 1, and velocity ratio is 205: 1, and flue gas is 5556 hours by the volume space velocity of beds 5
-1, the disturbance medium injected in the mixture of denitrfying agent and flue gas and 5.03 seconds before catalyst contacts.Record NO in the flue gas after the denitration
xContent be 45mg/Nm
3, NO
xConversion ratio be 91.8 weight %.
This embodiment is used to illustrate described denitration method for flue gas provided by the invention.
Adopt the denitrating flue gas equipment enforcement denitrating flue gas identical with embodiment 1, different is, adjust the position of opening in flue 1 of denitrfying agent device for supplying 3, making denitrfying agent device for supplying 3 the distance first vertical section a and 5 meters, horizontal segment b adjacent position in horizontal segment b is that the aqueous solution of urea of 39 weight % is sent in the flue (at this moment with concentration, the temperature of the mixture that produces after the above-mentioned contact is 700 ℃), making the ammonia nitrogen mol ratio in this mixture is 0.8: 1.This mixture temperature after about 3.4 seconds of having mended urea is reduced to about 400 ℃, and under this temperature with 6482h
-1Volume space velocity by beds 5.Record NO in the flue gas after the denitration
xContent be 100mg/Nm
3, NO
xConversion ratio be 71.4 weight %.
Claims (11)
1. denitration method for flue gas, it is characterized in that, this method is included under the flue gas SNCR condition, flue gas is contacted with denitrfying agent, obtain first mixture, in first mixture, mend denitrfying agent respectively and inject the disturbance medium, obtain second mixture, under flue gas SCR condition, second mixture is contacted with catalyst.
2. method according to claim 1 wherein, mends denitrfying agent earlier in first mixture, then, the disturbance medium that reinjects carries out disturbance to mending the denitrfying agent and first mixture of going into.
3. 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 first mixture is 0.001-0.1: 1, velocity ratio is 10-250: 1, and the disturbance medium injects in second mixture and 0.1 second before catalyst contacts at least.
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 first mixture.
7. method according to claim 1, wherein, described denitrfying agent is the material that can produce ammonia after ammonia or the heating, and the temperature of first mixture is higher at least 300 ℃ than the decomposition temperature of denitrfying agent when mending denitrfying agent, and time to the time interval that contacts with catalyst of mending denitrfying agent was at least 4 seconds.
8. according to claim 1 or 7 described methods, wherein, the amount of mending the denitrfying agent of going into makes denitrfying agent in second mixture and the NO in the flue gas
xThe ammonia nitrogen mol ratio be 0.5-1.1: 1.
9. method according to claim 1, wherein, the condition of described flue gas SNCR denitration comprises: the temperature that flue gas contacts with denitrfying agent is 950-1300 ℃, the time of contact is 0.1-2 second, the NO in denitrfying agent and the flue gas
xThe ammonia nitrogen mol ratio be 0.3-1.5: 1.
10. method according to claim 1, wherein, the selective-catalytic-reduction denitrified condition of described flue gas comprises: the temperature that second mixture contacts with catalyst is 280-420 ℃, the volume space velocity of flue gas is 200-20000 hour
-1
11. method according to claim 1, wherein, described catalyst is board-like catalyst or the honeycombed catalyst that contains metal oxide, and described metal oxide is 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, be benchmark with the total amount of catalyst, the content of described metal oxide is 1-5 weight %.
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