CN109758898A - Based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities - Google Patents
Based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities Download PDFInfo
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- CN109758898A CN109758898A CN201910130516.0A CN201910130516A CN109758898A CN 109758898 A CN109758898 A CN 109758898A CN 201910130516 A CN201910130516 A CN 201910130516A CN 109758898 A CN109758898 A CN 109758898A
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- hydrazine
- ammonium hydroxide
- denitrfying agent
- mixing
- storage tank
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 85
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000908 ammonium hydroxide Substances 0.000 title claims abstract description 68
- 238000002156 mixing Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003546 flue gas Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000779 smoke Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010612 desalination reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 50
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000032750 Device leakage Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities, it is uniformly mixed by ammonium hydroxide and hydrazine solution, in low smoke temperature, the mass fraction of ammonium hydroxide is 25%-65% in the mixing denitrfying agent, and the mass fraction for mixing hydrazine solution in denitrfying agent is 35%-75%.In low smoke temperature, ammonium hydroxide+hydrazine mixing denitrfying agent is prepared by preparation facilities and is pumped into the nozzle (41) of gun system (4), mixing denitrfying agent is injected in burner hearth after compressed nitrogen is atomized in nozzle carries out denitration reaction.The present invention is adapted to large range of furnace temperature by the concentration of change hydrazine, and the denitration of low fire box temperature incinerator is solved the problems, such as under the premise of not significantly improving equipment investment and operation cost.
Description
Technical field
The present invention relates to the method for denitration and preparation facilities of a kind of smoke denitrifier and its denitrfying agent more particularly to a kind of bases
In ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities.
Background technique
With the development of social economy and technology, different types of burning kiln and boiler are widely used in all trades and professions,
Bring is the generation of the flue gas of different contaminant components and physicochemical property therewith.
The NO generated in boiler, incinerator combustion processXThe decomposition of containing N organic matter of a part in fuel turns
Change, nitrogen of the another part in air generates under oxidizing atmosphere and hot conditions.NOx has NO, NO2、N2O、N2O3、
N2O7Variforms are waited, the NOx in fuel incineration flue gas is based on NO, and concentration increases sharply with temperature raising and high-temperature region
Gas residence time is longer, and NO production quantity is more.Low temperature is then conducive to NO2Generation.Although NOx usually with 95% NO and
5% NO2Composition, but generally all press 100% NO2It calculates, this is because NO passes through light under the conditions of the temperature less than 200 DEG C
Chemical reaction is converted to NO2.It is divided into according to the reaction type that nitrogen oxides produces mechanism:
(1) heating power type (thermal): referring under the environmental conditions such as oxygen, temperature, the N in air2And O2Reaction generates NOx's
Process.When ignition temperature is less than 1500 DEG C, NO production quantity very little；When greater than 1500 DEG C, every to improve 100 DEG C, reaction rate is mentioned
It is 6~7 times high.The generating principle of thermal NO x: 2N2+3O2→2NO2(g)+2NO(g)。
(2) fuel type (fuel): refer in combustion process, organic nitrogen is reduced into NH in fuel3, NH3And O2Chemical combination generates
The process of NOx.Since nitrogen molecular N ≡ N bond energy is more much bigger than C-N bond energy in organic matter, oxygen destroys C-N key first and generates
NOx generates 600~800 DEG C of temperature, sharply declines when being greater than 900 DEG C, therefore the influence of ignition temperature is little, and excess air
The influence of coefficient is significant, and as excess air coefficient α < 1, conversion rate of NOx is significantly reduced, and when α=0.7, conversion rate of NOx tends to
0.Fuel NOx generating principle:
CxHyOzNw+O2→CO2+H2O+NO2+ NO+ is imperfect combustion object.
(3) Quick-type (prompt): in combustion process, hydrocarbon combustion generates NOx.Also have and merge with heating power type,
It is referred to as heating power type.
Currently, except NO is reduced in source using technologies such as low nitrogen burningsXOutside yield, traditional gas denitrifying technology is main
It is divided into SNCR (selective non-catalytic reduction) denitration and SCR (selective catalytic reduction) denitration, difference place is whether use
Catalyst degradation reaction condition.General widely used denitrfying agent is urea or ammonium hydroxide, under certain reaction condition, by NOXAlso
Original is at N2With water.
SCR denitration technology reaction condition is more mitigated and (can be reacted using low temperature catalyst at 220 DEG C) and NOX
Removal efficiency is higher.But according to SCR technique, referring to the high dirt arrangement form of current coal-burning power plant's prevailing technology, then such as
Under the use condition of biomass electric power plant, because exhaust gas dust and its alkali metal (Na, K) content are higher, SCR catalyst will be caused to grind
Damage, blocking, or pollution, poisoning, to substantially reduce the service life of catalyst.And SCR process system high investment, and cigarette
Gas smoke temperature after bag filter is still not enough to support to complete catalytic reduction reaction, and a large amount of steam must be used to heat up, and brings fortune
The height of row cost is not looked forward to.So NO in many occasionsXThe lower SNCR of removal efficiency is still optimal selection.
It is its stringenter reaction temperature section using the drawbacks of SNCR denitration technology of urea or ammonium hydroxide: if using ammonia
Water needs to control smoke temperature within the scope of 850 DEG C -1050 DEG C, and the reaction time is greater than 1s；If also being needed using urea temperature window
Move up 50 DEG C.It is easier to realize in certain application fields (such as coal-powder boiler, glass furnace or smelting stove), but lower in some furnace temperature
(such as biomass boiler and waste incinerator) is very low using SNCR denitration efficiency under situation.
Summary of the invention
The purpose of the present invention is to provide a kind of based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation
Device is adapted to large range of furnace temperature, is not significantly improving equipment investment and operation cost by changing the concentration of hydrazine
Under the premise of solve the problems, such as the denitration of low fire box temperature incinerator.
The present invention is implemented as follows:
It is a kind of to be uniformly mixed based on ammonium hydroxide+hydrazine mixing denitrfying agent by ammonium hydroxide and hydrazine solution, in low smoke temperature feelings
Under condition, the mass fraction of ammonium hydroxide is 25%-65% in the mixing denitrfying agent, mixes the quality point of hydrazine solution in denitrfying agent
Number is 35%-75%.
The low smoke temperature is 550-750 DEG C.
A kind of denitration method for flue gas based on ammonium hydroxide+hydrazine mixing denitrfying agent passes through preparation dress in low smoke temperature
The nozzle for preparing ammonium hydroxide+hydrazine mixing denitrfying agent and being pumped into gun system is set, mixing denitrfying agent sprays after being atomized in nozzle
It penetrates and carries out denitration reaction in burner hearth.
A kind of preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent for denitration method for flue gas, including hydrazine storage
Tank, pipe-line mixer, gun system and tank used for storing ammonia store hydrazine solution in hydrazine storage tank, ammonium hydroxide are stored in tank used for storing ammonia, join
The outlet end of ammonia storage tank and tank used for storing ammonia is connect with the liquid feeding end of pipe-line mixer respectively, keeps ammonium hydroxide and hydrazine solution mixed in pipeline
Mixing denitrfying agent is sufficiently mixed into clutch；The outlet end of pipe-line mixer is connected to the liquid feeding end of gun system, gun system
Outlet end will mix denitrfying agent by several nozzles and spray, several nozzles are mounted in low smoke temperature burner hearth.
The preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes nitrogen preparation system, nitrogen preparation
System is connect with hydrazine storage tank and nozzle.
The gun system further includes several dosage dispensing cabinets, and the mixing denitrfying agent after dilution is through several dosage point
It is assigned in several nozzles with cabinet correspondence.
The preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes desalination water storage tank, desalination water storage tank
Demineralized water is stored, the outlet end of desalination water storage tank is connected to hydrazine storage tank.
Medicament tourie is connected on the hydrazine storage tank.
Compared with prior art, the present invention having the following beneficial effects:
1, the present invention is using the strong reducing property and lower denitration temperature for mixing hydrazine in denitrfying agent, in SNCR denitration technology
In widened denitration temperature range in burner hearth, improve denitration efficiency, reach national emission request.
2, preparation facilities of the invention is by adjusting the concentration and injection point for mixing denitrfying agent, to adapt to different burner hearths
Temperature and initial NOXConcentration.
3, preparation facilities of the invention is full-closed structure, guarantees to be discharged without exhaust gas waste water, and carry out by warning device
Leakage control, it is ensured that safety in utilization.
4, preparation facilities of the invention avoids hydrazine solution and flue gas from reacting in hydrazine storage tank by nitrogen, into one
Step improves the safety in utilization of hydrazine solution.
5, the present invention uses well-mixed hydrazine and ammonia spirit, and by nitrogen atomization in spray gun, low in burner hearth
It is insensitive to the height of oxygen content in warm area, reaction efficiency is greatly strengthened, stoichiometric ratio is reduced.
The present invention is for furnace temperature is lower or initial NOXHigher operating condition is creatively made using ammonium hydroxide+hydrazine mixed solution
It is reacted for denitrfying agent, the extremely strong reproducibility of the hydrazine utilized, reaction temperature window lower (600-750 DEG C), flue gas oxygen contain
Temperature range such as moves up at the properties when amount reduces, and ammonium hydroxide and hydrazine is used in combination, has greatly widened the reaction temperature of denitration in the stove
Section, while the reaction time is extended, low fire box temperature is solved under the premise of not significantly improving equipment investment and operation cost
The denitration problem of incinerator.
Detailed description of the invention
Fig. 1 is that the present invention is based on the main views of the preparation facilities of ammonium hydroxide+hydrazine mixing denitrfying agent；
Fig. 2 is that the present invention is based on the main views of the gun system of the preparation facilities of ammonium hydroxide+hydrazine mixing denitrfying agent.
In figure, 1 hydrazine storage tank, 2 nitrogen preparation systems, 3 pipe-line mixers, 4 gun systems, 41 nozzles, the distribution of 42 dosage
Cabinet, 5 tank used for storing ammonia, 6 desalination water storage tanks, 7 medicament touries.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Refer to attached drawing 1 and attached drawing 2, a kind of preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent, including hydrazine storage
Tank 1, pipe-line mixer 3, gun system 4 and tank used for storing ammonia 5 store hydrazine solution in hydrazine storage tank 1, store in tank used for storing ammonia 5
The outlet end of ammonium hydroxide, hydrazine storage tank 1 and tank used for storing ammonia 5 is connect with the liquid feeding end of pipe-line mixer 3 respectively, keeps ammonium hydroxide and hydrazine molten
Liquid is sufficiently mixed into mixing denitrfying agent in pipe-line mixer 3；The outlet end of pipe-line mixer 3 distributes main pipe connection by spray gun
To the liquid feeding end of gun system 4, the outlet end of gun system 4 will mix denitrfying agent by several nozzles 41 and spray, several
Nozzle 41 is mounted in low smoke temperature burner hearth, it is preferred that the temperature that the position of nozzle 41 should make denitrfying agent spray into region is most suitable
The progress of suitable denitration reaction, and escape ammonia is smaller to the corrosion impact of boiler heating surface.
The preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes nitrogen preparation system 2, nitrogen preparation
System 2 is connect with hydrazine storage tank 1 and nozzle 41, can play the role of nitrogen protection in hydrazine storage tank 1, and hydrazine is avoided to meet oxygen hair
Life reacts and causes serious safety accident, and nitrogen can be used for the mixing denitrfying agent in atomizer 41, it is preferred that nozzle 41
Double fluid atomization nozzle can be used.
The gun system 4 further includes several dosage dispensing cabinets 42, and the mixing denitrfying agent after dilution is passed through by pipeline
Several dosage dispensing cabinets 42 correspondence is assigned in several nozzles 41, can accurately control the dosage that each nozzle 41 sprays.
The preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes desalination water storage tank 6, desalination water storage tank
6 storage demineralized waters, the outlet end of desalination water storage tank 6 are connected to hydrazine storage tank 1 by pipeline, can be used for being added in hydrazine solution
Demineralized water, demineralized water are adjusted according to required concentration and are matched, and are uniformly mixed and are sufficiently dissolved with even right solution in hydrazine storage tank 1
Afterwards, hydrazine storage tank 1 is pumped out, is uniformly mixed in pipe-line mixer 3 with ammonia spirit.It is conveyed when system is run by denitrfying agent
It is pumped to gun system 4.
It is connected with medicament tourie 7 on the hydrazine storage tank 1, due to adding medicament all companions in hydrazine storage tank 1 every time
As the air above liquid level is discharged, and need to lead so cannot directly empty containing the hydrazine vapored away in this air
Hydrazine is sponged in medicament tourie 7.Absorption pattern is exactly that exhaust pipe reaches absorbent liquid level hereinafter, rising in bubble
It is absorbed in the process.Preferably, flanged joint can be used in the connection type of medicament tourie 7 and hydrazine storage tank 1.
According to initial nitrous oxides concentration and required removal efficiency in burner hearth flue gas, the mixing denitration of concentration needed for configuring
Agent solution can be adjusted as needed.In view of hydrazine has toxicity, and there is higher vapor pressure and smoke feature,
In preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent, all connecting pipes, the pump housing, storage tank etc. are all using totally-enclosed
Structure and totally-enclosed conveying, it is ensured that no exhaust gas waste water discharge, and in the site setting leakage alarms dress that medicament escape may occur
It sets, for alarm to be sent to external PLC/DCS control system, and is acted by interlocking and carry out leakage control.
It is a kind of to be uniformly mixed based on ammonium hydroxide+hydrazine mixing denitrfying agent by ammonium hydroxide and hydrazine solution, it is lower in smoke temperature
In the case of (550-750 DEG C), the mass fraction of ammonium hydroxide is 25%-65% in the mixing denitrfying agent, mixes and joins in denitrfying agent
The mass fraction of ammonia solution is 35%-75%.If smoke temperature is higher than 750 DEG C, denitration efficiency as needed can suitably reduce hydrazine
Solution usage amount improves ammonium hydroxide ratio.The present invention say the mass concentration of the ammonium hydroxide used for 20%, the mass concentration of hydrazine solution
It is 40%.
A kind of denitration method for flue gas based on ammonium hydroxide+hydrazine mixing denitrfying agent, specific steps are as follows: lower in smoke temperature
In the case of (550-750 DEG C), the nozzle that ammonium hydroxide+hydrazine mixes denitrfying agent and is pumped into gun system 4 is prepared by preparation facilities
41, mixing denitrfying agent is injected in burner hearth after compressed nitrogen is atomized in nozzle 41 carries out denitration reaction, by adjusting mixing
The concentration and injection point of denitrfying agent, to adapt to different fire box temperatures and initial NOXConcentration.
Under the conditions of lower smoke temperature, the present invention carries out the chemical formula of denitration reaction such as after mixing using ammonium hydroxide and hydrazine solution
Under:
Ammonium hydroxide: 4NH3+4NO+O2→4N2+6H2O
Hydrazine: N2H4+2NO→2N2+2H2O
The solution of the present invention is similarly applied in the SNCR using urea, is taken off after urea is mixed with hydrazine solution
Nitre reaction, the chemical reaction that urea and hydrazine solution occur in burner hearth are as follows:
Urea: N2H4CO+2NO→2N2+2H2O+CO
Hydrazine: N2H4+2NO→2N2+2H2O
Since hydrazine solution and ammonium hydroxide are sufficiently mixed in pipe-line mixer 3 using preceding, and by nitrogen in gun system 4
Nitrogen atomization prepared by gas preparation system 2, it is insensitive to the height of oxygen content in burner hearth low-temperature space, it is anti-denitration can be substantially reduced
Temperature requirement is answered, reaction efficiency is greatly strengthened, reduces stoichiometric ratio, improves denitration efficiency.
Embodiment 1: biomass recirculating fluidized bed boiler denitrating flue gas
The concentration of emission of NOx is in 120~150mg/Nm when certain recirculating fluidized bed biomass boiler does not take any measure3It
Between；In most cases in 130mg/Nm3More than；Temperature inside burner hearth is between 600~700 DEG C, before pendant superheater
Smoke temperature is 550 DEG C.Excess air coefficient is 1.4 or so at furnace outlet；The SNCR denitration measure using ammonium hydroxide as denitrfying agent is taken,
In NH3: when the stoichiometric ratio of NOx=1.5, the concentration of NOx is still in 120~140mg/Nm in smoke evacuation3Between, almost without de-
Nitre effect is not able to satisfy newest standards NOx emission lower than 100mg/Nm3Requirement；Using mixing denitrfying agent of the invention, only exist
Hydrazine solution (concentration 40wt%) is added in original ammonium hydroxide system, is as ratio shared by denitrfying agent, ammonium hydroxide N after mixing
50%；Denitrfying agent: the stoichiometric ratio of NOx is 1.2 (with 150mg/Nm3For calculating benchmark)；The temperature of measuring point, oxygen behind spout
The discharge amount of NOx is shown in Table 1 in the volumetric concentration of amount, smoke evacuation.
Denitration efficiency when in 1 burner hearth of table using ammonium hydroxide, hydrazine mixture as denitrfying agent
Under the conditions of lower fire box temperature, denitration efficiency can be made to meet discharge using mixing denitrfying agent of the invention and wanted
It asks, and without NH in flue gas3Escape.
Embodiment 2: biomass stove grate furnace denitration of boiler smoke
The concentration of emission of NOx is in 220~250mg/Nm when certain biomass stove grate furnace boiler does not take any measure3Between；
In most cases in 230mg/Nm3More than；Smoke temperature of the temperature between 730~870 DEG C, before pendant superheater inside burner hearth
It is 750 DEG C.Excess air coefficient is 1.4 or so at furnace outlet；The SNCR denitration measure using ammonium hydroxide as denitrfying agent is taken,
NH3: when the stoichiometric ratio of NOx=1.8, the concentration of NOx is still in 120~150mg/Nm in smoke evacuation3Between, it is not able to satisfy newest
Standard NOx emission is lower than 100mg/Nm3Requirement；Using mixing denitrfying agent of the invention, only it is added in original ammonium hydroxide system
Hydrazine solution (concentration 40wt%), after mixing as ratio shared by denitrfying agent, ammonium hydroxide N be 80%；Denitrfying agent: the change of NOx
Learning equivalent proportion is 1.2 (with 250mg/Nm3For calculating benchmark)；The volumetric concentration of the temperature, oxygen amount of measuring point behind spout, in smoke evacuation
The discharge amount of NOx is shown in Table 2.
Denitration efficiency when in 2 burner hearth of table using ammonium hydroxide, hydrazine mixture as denitrfying agent
By table as it can be seen that using not only discharge is completely up to standard after mixing denitrfying agent progress denitration reaction of the invention, but also
Without NH in flue gas3Escape.
Embodiment 3: recycle fluidized-bed combustion boiler denitrating flue gas
The original nitrous oxides concentration 300mg/Nm of certain recycle fluidized-bed combustion boiler3, denitrating technique uses SNCR, with urea
Solution (40% mass concentration) is reducing agent, designs denitration efficiency 35%.Experiment uses mixing denitrfying agent of the invention for reduction
Agent, the mass fraction for mixing ammonia spirit (20% mass concentration) in denitrfying agent is 80%, hydrazine solution (40% mass concentration)
Mass fraction be 20%, mixing denitrfying agent and nitrogen oxides stoichiometric ratio be 1.2, experimental data is shown in Table 3:
Table 3: denitration efficiency when in burner hearth using ammonium hydroxide, hydrazine mixture as denitrfying agent
By table as it can be seen that in the same circumstances, denitration efficiency, and nothing can be substantially improved using mixing denitrfying agent of the invention
The escaping of ammonia problem.
Embodiment 4: rubbish grate furnace denitration of boiler smoke
Jiangsu rubbish grate furnace boiler original beginning nitrous oxides concentration 400-600mg/Nm3, denitrating technique use SNCR, with
Ammonium hydroxide is reducing agent, designs denitration efficiency 55%, and smoke emissioning concentration should be less than referring to EU2010, nitrogen oxides exit concentration
200mg/Nm3, but since original nitrous oxides concentration momentary fluctuation is larger, it causes discharged nitrous oxides concentration that cannot stablize and reaches
Mark, therefore need to take measures to discharge flue gas stably reaching standard.It uses ammonium hydroxide/hydrazine solution for reducing agent, mixes ammonium hydroxide in denitrfying agent
Solution (20% mass concentration) mass fraction 90%, hydrazine solution (40% mass concentration) mass fraction 10% mix denitrfying agent
It is 1 with nitrogen oxides stoichiometric ratio, experimental data is shown in Table 4:
Table 4: denitration efficiency when in burner hearth using ammonium hydroxide, hydrazine mixture as denitrfying agent
Mixing denitrfying agent of the invention is in the case where hydrazine mass fraction very little it can be seen from table, in higher temperatures
Section is spent, it is horizontal also to can achieve higher denitration.
The above is merely preferred embodiments of the present invention, it is not intended to limit the protection scope of invention, it is therefore, all at this
Any modification, equivalent replacement, improvement and so within the spirit and principle of invention, should be included in protection scope of the present invention
Within.
Claims (8)
1. it is a kind of based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: be uniformly mixed by ammonium hydroxide and hydrazine solution,
In the case of low smoke temperature, the mass fraction of ammonium hydroxide is 25%-65% in the mixing denitrfying agent, mixes hydrazine solution in denitrfying agent
Mass fraction be 35%-75%.
2. it is according to claim 1 based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: the low smoke temperature is
550-750℃。
3. a kind of denitration method for flue gas according to claim 1 or 2 based on ammonium hydroxide+hydrazine mixing denitrfying agent, special
Sign is: in low smoke temperature, preparing ammonium hydroxide+hydrazine mixing denitrfying agent by preparation facilities and is pumped into gun system (4)
Nozzle (41), mixing denitrfying agent are injected in burner hearth after being atomized in nozzle (41) and carry out denitration reaction.
4. a kind of preparation dress based on ammonium hydroxide+hydrazine mixing denitrfying agent for denitration method for flue gas as claimed in claim 3
It sets, it is characterized in that: including hydrazine storage tank (1), pipe-line mixer (3), gun system (4) and tank used for storing ammonia (5), hydrazine storage tank
(1) hydrazine solution is stored in, and ammonium hydroxide, the outlet end difference of hydrazine storage tank (1) and tank used for storing ammonia (5) are stored in tank used for storing ammonia (5)
It is connect with the liquid feeding end of pipe-line mixer (3), so that ammonium hydroxide and hydrazine solution is sufficiently mixed into mixing in pipe-line mixer (3) de-
Nitre agent；The outlet end of pipe-line mixer (3) is connected to the liquid feeding end of gun system (4), gun system (4) if outlet end by
Dry nozzle (41) will mix denitrfying agent and spray, several nozzles (41) are mounted in low smoke temperature burner hearth.
5. the preparation facilities according to claim 4 based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: described
Preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes nitrogen preparation system (2), nitrogen preparation system (2) and connection
Ammonia storage tank (1) and nozzle (41) connection.
6. the preparation facilities according to claim 4 based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: described
Gun system (4) further includes several dosage dispensing cabinets (42), and the mixing denitrfying agent after dilution is through several dosage dispensing cabinets
(42) correspondence is assigned in several nozzles (41).
7. the preparation facilities according to claim 4 based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: described
Preparation facilities based on ammonium hydroxide+hydrazine mixing denitrfying agent further includes desalination water storage tank (6), and desalination water storage tank (6) stores desalination
Water, the outlet end of desalination water storage tank (6) are connected to hydrazine storage tank (1).
8. the preparation facilities according to claim 4 based on ammonium hydroxide+hydrazine mixing denitrfying agent, it is characterized in that: described
Medicament tourie (7) are connected on hydrazine storage tank (1).
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