CN209828701U - Preparation facilities of mixed denitrifier based on aqueous ammonia + hydrazine - Google Patents
Preparation facilities of mixed denitrifier based on aqueous ammonia + hydrazine Download PDFInfo
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- CN209828701U CN209828701U CN201920230289.4U CN201920230289U CN209828701U CN 209828701 U CN209828701 U CN 209828701U CN 201920230289 U CN201920230289 U CN 201920230289U CN 209828701 U CN209828701 U CN 209828701U
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Abstract
The utility model discloses a preparation facilities of mixed denitrifier based on aqueous ammonia + hydrazine, including hydrazine storage tank (1), line mixer (3), spray gun system (4) and aqueous ammonia storage tank (5), store the hydrazine solution in the hydrazine storage tank, store the aqueous ammonia in the aqueous ammonia storage tank, the liquid outlet end of hydrazine storage tank and aqueous ammonia storage tank is connected with the feed liquor end of line mixer respectively, makes aqueous ammonia and hydrazine solution fully mix into mixed denitrifier in the line mixer; the liquid outlet end of the pipeline mixer is connected to the liquid inlet end of the spray gun system, the liquid outlet end of the spray gun system sprays the mixed denitration agent through a plurality of nozzles (41), and the plurality of nozzles are installed in the low smoke temperature hearth. The utility model discloses can prepare the denitrifier of being made by aqueous ammonia and hydrazine mixture, can adapt to great furnace temperature on a large scale when flue gas denitration operation, solve the denitration problem that low furnace temperature burns burning furnace under the prerequisite of not showing improve equipment investment and operation cost.
Description
Technical Field
The utility model relates to a preparation facilities of flue gas denitration agent especially relates to a preparation facilities of mixed denitration agent based on aqueous ammonia + hydrazine.
Background
With the development of social economy and technology, different types of incineration kilns and boilers are widely used in various industries, and along with the development of smoke with different pollutant components and physical and chemical properties, the smoke is generated.
NO produced in the combustion process of boiler and incineratorXOne part is from the decomposition and conversion of the N-containing organic matter in the fuel, and the other part is from the generation of nitrogen in the air under the oxidizing atmosphere and high temperature conditions. NOx has NO and NO2、N2O、N2O3、N2O7And in various forms, NOx in the fuel incineration flue gas is mainly NO, the concentration of the NOx is rapidly increased along with the increase of the temperature, and the longer the residence time of the flue gas in a high-temperature area is, the more NO is generated. Low temperature favors NO2And (4) generating. Although NOx is typically 95% NO and 5% NO2Composition, but generally expressed as 100% NO2This is calculated because NO is converted to NO by photochemical reactions at temperatures less than 200 deg.C2. The reaction types according to the nitrogen oxide production mechanism are classified into:
(1) thermal type (thermal): refers to N in the air under the environmental conditions of oxygen, temperature and the like2And O2The process of reaction to form NOx. When the combustion temperature is less than 1500 ℃, the generation amount of NO is very small; when the temperature is more than 1500 ℃, the reaction rate is increased by 6-7 times every time the temperature is increased by 100 ℃. Principle of formation of thermal NOx: 2N2+3O2→2NO2(g)+2NO(g)。
(2) Fuel type (fuel): means that organic nitrogen in the fuel is reduced to NH during combustion3，NH3And O2Combining to form NOx. Due to the N.ident.N bond energy ratio of nitrogen moleculeSince the organic matter has a much larger C — N bond energy, oxygen first breaks the C — N bond to generate NOx, the generation temperature is 600 to 800 ℃, and when the temperature is higher than 900 ℃, the influence of the combustion temperature is small, the influence of the excess air factor is significant, when the excess air factor α is lower than 1, the NOx conversion rate is significantly reduced, and when α is 0.7, the NOx conversion rate tends to 0. Fuel NOx generation principle:
CxHyOzNw+O2→CO2+H2O+NO2+ NO + incomplete combustion.
(3) Rapid (prompt): during combustion, hydrocarbons are combusted to form NOx. There are also combinations with the thermodynamic type, collectively referred to as the thermodynamic type.
At present, the technology such as low-nitrogen combustion is adopted to reduce NO at the sourceXBesides the output, the traditional flue gas denitration technology is mainly divided into SNCR (selective non-catalytic reduction) denitration and SCR (selective catalytic reduction) denitration, and the difference lies in whether a catalyst is used for reducing the reaction condition. The denitration agent which is widely used generally is urea or ammonia water, and NO is reacted under certain reaction conditionsXReduction to N2And water.
The SCR denitration technology has mild reaction conditions (low-temperature catalyst can react at 220 ℃) and NOXThe removal rate is high. However, if the SCR process is adopted, referring to the high dust arrangement form of the mainstream process of the current coal-fired power plant, under the use conditions of a biomass power plant, the SCR catalyst is abraded, blocked, polluted or poisoned due to high content of flue gas dust and alkali metals (Na, K), so that the service life of the catalyst is greatly reduced. And the investment of an SCR process system is high, the temperature of the flue gas after the flue gas is placed in a bag-type dust collector is not enough to support the completion of catalytic reduction reaction, and a large amount of steam is needed to be used for heating, so that the running cost is high. So that NO is present in many casesXThe SNCR with lower removal rates is still the optimal choice.
The SNCR denitration technique using urea or ammonia water has a disadvantage in that it has a relatively strict reaction temperature interval: if ammonia water is used, the smoke temperature needs to be controlled within the range of 850-1050 ℃, and the reaction time is more than 1 s; if urea is used, the temperature window is also shifted up by 50 ℃. The method is easy to realize in certain application fields (such as a pulverized coal furnace, a glass furnace or a smelting furnace kiln), but the SNCR denitration efficiency is quite low under the condition of low furnace temperature (such as a biomass boiler and a garbage incinerator).
Disclosure of Invention
An object of the utility model is to provide a preparation facilities of mixed denitration agent based on aqueous ammonia + hydrazine can prepare the denitration agent of being made by aqueous ammonia and hydrazine mixture, can adapt to great oven temperature on a large scale when flue gas denitration operation, solves the denitration problem that low furnace temperature burns burning furnace under the prerequisite of improvement equipment investment and operation cost is not showing.
The utility model discloses a realize like this:
a preparation device of a mixed denitration agent based on ammonia water and hydrazine comprises a hydrazine storage tank, a pipeline mixer, a spray gun system and an ammonia storage tank, wherein a hydrazine solution is stored in the hydrazine storage tank, the ammonia water is stored in the ammonia storage tank, and the liquid outlet ends of the hydrazine storage tank and the ammonia storage tank are respectively connected with the liquid inlet end of the pipeline mixer, so that the ammonia water and the hydrazine solution are fully mixed into the mixed denitration agent in the pipeline mixer; the liquid outlet end of the pipeline mixer is connected to the liquid inlet end of the spray gun system, the liquid outlet end of the spray gun system sprays the mixed denitration agent through a plurality of nozzles, and the plurality of nozzles are installed in the low-smoke-temperature hearth.
The preparation device of the mixed denitration agent based on the ammonia water and the hydrazine further comprises a nitrogen preparation system, and the nitrogen preparation system is connected with the hydrazine storage tank and the nozzle.
The spray gun system also comprises a plurality of dosage distribution cabinets, and the diluted mixed denitration agent is correspondingly distributed to a plurality of nozzles through the dosage distribution cabinets.
The preparation device of the mixed denitration agent based on the ammonia water and the hydrazine further comprises a demineralized water storage tank, wherein the demineralized water storage tank stores demineralized water, and the liquid outlet end of the demineralized water storage tank is connected to the hydrazine storage tank.
The hydrazine storage tank is connected with a medicament absorption tank.
Compared with the prior art, the utility model, following beneficial effect has:
1. the preparation device of the utility model is provided with a transferThe concentration and the injection point position of the mixed denitration agent are adjusted to adapt to different hearth temperatures and initial NOXAnd (4) concentration.
2. The utility model discloses a preparation facilities is totally enclosed structure, guarantees no waste gas waste water discharge to carry out leakage control through alarm device, ensure the safety in utilization.
3. The utility model discloses a preparation facilities avoids hydrazine solution and flue gas to react through nitrogen gas in the hydrazine storage tank, further improves hydrazine solution's safety in utilization.
4. The utility model discloses the mixed denitration agent of preparation receives nitrogen gas atomizing in the spray gun, and is insensitive to the height of oxygen content in furnace low-temperature region, has strengthened reaction efficiency greatly, has reduced the stoichiometric ratio.
The utility model discloses can be to lower or initial NO of furnace temperatureXThe ammonia water and hydrazine mixed denitration agent is prepared under a high working condition, and the properties of strong reducibility of hydrazine, low reaction temperature window (600-750 ℃), upward shift of a temperature interval when the oxygen content of flue gas is reduced and the like are utilized, so that the reaction temperature interval of denitration in the incinerator is greatly widened by the ammonia water and hydrazine based mixed denitration agent, the reaction time is prolonged, and the denitration problem of the low-hearth-temperature incinerator is solved on the premise of not remarkably improving the equipment investment and the operation cost.
Drawings
FIG. 1 is a front view of a device for preparing a mixed denitration agent based on ammonia water and hydrazine;
fig. 2 is the utility model discloses a preparation facilities's spray gun system based on aqueous ammonia + hydrazine mixed denitrifier's front view.
In the figure, 1 hydrazine storage tank, 2 nitrogen preparation system, 3 pipeline mixer, 4 spray gun system, 41 spray nozzles, 42 dosage distribution cabinet, 5 ammonia storage tank, 6 demineralized water storage tank, 7 medicament absorption tank.
Detailed Description
The invention will be further explained with reference to the drawings and the specific embodiments.
Referring to fig. 1 and 2, a preparation apparatus for a mixed denitration agent based on ammonia water and hydrazine comprises a hydrazine storage tank 1, a pipeline mixer 3, a spray gun system 4 and an ammonia water storage tank 5, wherein a hydrazine solution is stored in the hydrazine storage tank 1, ammonia water is stored in the ammonia water storage tank 5, and liquid outlet ends of the hydrazine storage tank 1 and the ammonia water storage tank 5 are respectively connected with a liquid inlet end of the pipeline mixer 3, so that the ammonia water and the hydrazine solution are fully mixed into the mixed denitration agent in the pipeline mixer 3; the liquid outlet end of the pipeline mixer 3 is connected to the liquid inlet end of the spray gun system 4 through a spray gun distribution main pipe, the liquid outlet end of the spray gun system 4 sprays the mixed denitration agent through a plurality of nozzles 41, the plurality of nozzles 41 are installed in the low smoke temperature hearth, preferably, the arrangement positions of the nozzles 41 enable the temperature of the denitration agent spraying area to be optimum for denitration reaction, and the corrosion influence of escaping ammonia on the heating surface of the boiler is small.
The preparation device of the mixed denitration agent based on the ammonia water and the hydrazine further comprises a nitrogen preparation system 2, the nitrogen preparation system 2 is connected with the hydrazine storage tank 1 and the nozzle 41, the nitrogen protection effect can be achieved in the hydrazine storage tank 1, serious safety accidents caused by the reaction of the hydrazine in the presence of oxygen are avoided, the nitrogen can also be used for the mixed denitration agent in the atomizing nozzle 41, and preferably, the nozzle 41 can adopt a double-fluid atomizing nozzle.
The spray gun system 4 further comprises a plurality of dosage distribution cabinets 42, the diluted mixed denitration agent is correspondingly distributed to the plurality of nozzles 41 through the plurality of dosage distribution cabinets 42 through pipelines, and the dosage sprayed by each nozzle 41 can be accurately controlled.
Preparation facilities of mixed denitration agent based on aqueous ammonia + hydrazine still include demineralized water storage tank 6, demineralized water is stored to demineralized water storage tank 6, the play liquid end of demineralized water storage tank 6 passes through pipe connection to hydrazine storage tank 1, can be used to add demineralized water in the hydrazine solution, demineralized water is according to required concentration adjustment ratio, in hydrazine storage tank 1 with even and fully dissolve the back of burning solution misce bene, the pump is sent out hydrazine storage tank 1, with aqueous ammonia solution misce bene in pipeline mixer 3. The system is operated by a denitrifier delivery pump to the lance system 4.
The medicament absorption tank 7 is connected to the hydrazine storage tank 1, and since the medicament added to the hydrazine storage tank 1 every time is discharged along with the air above the liquid level, and the air contains volatilized hydrazine, the hydrazine cannot be directly emptied, and the hydrazine needs to be absorbed by the medicament absorption tank 7. The absorption mode is that the exhaust pipeline extends to the position below the liquid level of the absorbent, and the absorption is carried out in the process of rising bubbles. Preferably, the medicament absorption tank 7 and the hydrazine storage tank 1 are connected by a flange.
According to the initial nitrogen oxide concentration in the hearth flue gas and the required removal efficiency, the mixed denitration agent solution with the required concentration is prepared and can be adjusted as required. Considering that hydrazine has toxicity and has high vapor pressure and fuming characteristics, in the preparation device of the mixed denitration agent based on ammonia water and hydrazine, all connecting pipelines, a pump body, a storage tank and the like are in a fully-closed structure and are in fully-closed conveying, no waste gas and waste water are discharged, and a leakage alarm device is arranged at a point where the agent possibly escapes and is used for sending an alarm to an external PLC/DCS control system and carrying out leakage control through interlocking action.
The utility model discloses a mixed denitration agent based on aqueous ammonia + hydrazine of preparation facilities preparation is formed by aqueous ammonia and hydrazine solution homogeneous mixing, under the lower (550) 750 ℃ C. of smoke temperature condition, mixed denitration agent in the mass fraction of aqueous ammonia be 25% -65%, mixed denitration agent in the mass fraction of hydrazine solution be 35% -75%. If the smoke temperature is higher than 750 ℃, the usage amount of the hydrazine solution can be properly reduced according to the required denitration efficiency, and the proportion of the ammonia water is improved. The mass concentration of the ammonia water adopted by the utility model is 20 percent, and the mass concentration of the hydrazine solution is 40 percent.
The utility model discloses the mixed denitrifier based on aqueous ammonia + hydrazine of preparation is applied to flue gas denitration method, and its concrete step is: under the condition that the smoke temperature is low (550-XAnd (4) concentration.
Under the condition of lower smoke temperature, the utility model discloses a chemical formula that carries out denitration reaction after aqueous ammonia and hydrazine solution mix is as follows:
ammonia water: 4NH3+4NO+O2→4N2+6H2O
Hydrazine: n is a radical of2H4+2NO→2N2+2H2O
The utility model discloses an in the SNCR that adopts urea equally can be applied to the scheme, carry out denitration reaction after mixing urea and hydrazine solution, the chemical reaction that urea and hydrazine solution take place in furnace is as follows:
urea: n is a radical of2H4CO+2NO→2N2+2H2O+CO
Hydrazine: n is a radical of2H4+2NO→2N2+2H2O
Because the hydrazine solution and the ammonia water are fully mixed in the pipeline mixer 3 before being used, and are atomized by the nitrogen prepared by the nitrogen preparation system 2 in the spray gun system 4, the hydrazine solution and the ammonia water are insensitive to the oxygen content in the low-temperature area of the hearth, the requirement on the denitration reaction temperature can be greatly reduced, the reaction efficiency is greatly enhanced, the stoichiometric ratio is reduced, and the denitration efficiency is improved.
Example 1: flue gas denitration of biomass circulating fluidized bed boiler
When no measures are taken by a certain circulating fluidized bed biomass boiler, the emission concentration of NOx is 120-150 mg/Nm3To (c) to (d); in most cases at 130mg/Nm3The above; the temperature in the hearth is 600-700 ℃, and the smoke temperature before the platen superheater is 550 ℃. The excess air coefficient at the outlet of the hearth is about 1.4; adopting SNCR denitration measure using ammonia water as denitration agent in NH3: when the stoichiometric ratio of NOx is 1.5, the concentration of NOx in the exhaust gas is still 120-140 mg/Nm3Meanwhile, the denitration effect is almost not achieved, and the NOx emission which cannot meet the latest standard is lower than 100mg/Nm3The requirements of (1); adopt the utility model discloses a mix denitrifier, only add hydrazine solution (concentration is 40 wt%) in original aqueous ammonia system, mix the back as denitrifier, the shared proportion of aqueous ammonia N is 50%; a denitration agent: NOx stoichiometric ratio of 1.2 (at 150 mg/Nm)3As a basis for calculation); the temperature, the volume concentration of oxygen, and the amount of NOx emitted from the exhaust gas measured at the rear of the nozzle are shown in table 1.
TABLE 1 denitration efficiency when ammonia water and hydrazine mixture are used as denitration agent in furnace
Under the lower furnace temperature condition, use the utility model discloses a mixed denitration agent can make denitration efficiency satisfy the emission requirement, and does not have NH in the flue gas3And escape.
Example 2 denitration of flue gas of Biomass grate boiler
When no measures are taken by a certain biomass grate furnace boiler, the emission concentration of NOx is 220-250 mg/Nm3To (c) to (d); in most cases at 230mg/Nm3The above; the temperature in the hearth is 730-870 ℃, and the smoke temperature before the platen superheater is 750 ℃. The excess air coefficient at the outlet of the hearth is about 1.4; adopting SNCR denitration measure using ammonia water as denitration agent in NH3: when the stoichiometric ratio of NOx is 1.8, the concentration of NOx in the exhaust gas is still 120-150 mg/Nm3In between, the latest standard NOx emissions that cannot be met are less than 100mg/Nm3The requirements of (1); adopt the utility model discloses a mix denitrifier, only add hydrazine solution (concentration is 40 wt%) in original aqueous ammonia system, mix the back as denitrifier, the shared proportion of aqueous ammonia N is 80%; a denitration agent: NOx stoichiometric ratio of 1.2 (at 250 mg/Nm)3As a basis for calculation); the temperature, the volume concentration of oxygen, and the amount of NOx emitted from the exhaust gas measured at the rear of the nozzle are shown in table 2.
TABLE 2 denitration efficiency when ammonia water and hydrazine mixture are used as denitration agent in furnace
It is visible by the table, adopt the utility model discloses a mix denitration agent not only discharge completely up to standard after carrying out the denitration reaction, do not have NH in the flue gas moreover3And escape.
Example 3: flue gas denitration of garbage circulating fluidized bed boiler
The original nitrogen oxide concentration of a certain garbage circulating fluidized bed boiler is 300mg/Nm3The denitration process adopts SNCR, takes urea solution (with the mass concentration of 40%) as a reducing agent, and designs the denitration efficiency to be 35%. The experiment is adopted the utility model discloses a mixed denitration agent is the reductant, and the mass fraction of ammonia water solution (20% mass concentration) is 80% in the mixed denitration agent, and the mass fraction of hydrazine solution (40% mass concentration) is 20%, and mixed denitration agent is 1.2 with nitrogen oxide stoichiometric ratio, and the experimental data sees table 3:
table 3: denitration efficiency when ammonia water and hydrazine mixture are used as denitration agent in hearth
It is seen by the table, under the same conditions, use the utility model discloses a mixed denitration agent can promote denitration efficiency by a wide margin, and does not have ammonia escape problem.
Example 4: flue gas denitration of garbage grate boiler
The original nitrogen oxide concentration of the grate boiler of the garbage in Jiangsu is 400-fold and 600mg/Nm3The denitration process adopts SNCR, ammonia water is used as a reducing agent, the denitration efficiency is designed to be 55%, the flue gas emission concentration refers to EU2010, and the outlet concentration of nitrogen oxides is less than 200mg/Nm3However, the concentration of the nitrogen oxides cannot reach the standard stably due to the large instantaneous fluctuation of the original concentration of the nitrogen oxides, so measures are needed to ensure that the smoke gas can reach the standard stably. The ammonia water/hydrazine solution is used as a reducing agent, the mass fraction of the ammonia water solution (20 mass percent concentration) in the mixed denitration agent is 90%, the mass fraction of the hydrazine solution (40 mass percent concentration) is 10%, the stoichiometric ratio of the mixed denitration agent to the nitric oxide is 1, and the experimental data are shown in Table 4:
table 4: denitration efficiency when ammonia water and hydrazine mixture are used as denitration agent in hearth
As can be seen from the table, the utility model discloses a mixed denitration agent also can reach higher denitration level at higher temperature interval under the very little condition of hydrazine mass fraction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the scope of the present invention, therefore, any modifications, equivalents, improvements, etc. made within the spirit and principles of the present invention should be included within the scope of the present invention.
Claims (5)
1. The utility model provides a preparation facilities of mixed denitrifier based on aqueous ammonia + hydrazine, characterized by: the denitration agent comprises a hydrazine storage tank (1), a pipeline mixer (3), a spray gun system (4) and an ammonia water storage tank (5), wherein a hydrazine solution is stored in the hydrazine storage tank (1), ammonia water is stored in the ammonia water storage tank (5), and liquid outlet ends of the hydrazine storage tank (1) and the ammonia water storage tank (5) are respectively connected with a liquid inlet end of the pipeline mixer (3), so that the ammonia water and the hydrazine solution are fully mixed into a mixed denitration agent in the pipeline mixer (3); the liquid outlet end of the pipeline mixer (3) is connected to the liquid inlet end of the spray gun system (4), the liquid outlet end of the spray gun system (4) sprays mixed denitration agent through a plurality of nozzles (41), and the plurality of nozzles (41) are installed in the low smoke temperature hearth.
2. The apparatus for preparing mixed denitration agent based on ammonia water + hydrazine as claimed in claim 1, wherein: the preparation device of the mixed denitration agent based on the ammonia water and the hydrazine further comprises a nitrogen preparation system (2), and the nitrogen preparation system (2) is connected with the hydrazine storage tank (1) and the nozzle (41).
3. The apparatus for preparing a mixed denitration agent based on ammonia water + hydrazine according to claim 1 or 2, wherein: the spray gun system (4) further comprises a plurality of dosage distribution cabinets (42), and the diluted mixed denitration agent is correspondingly distributed to the plurality of nozzles (41) through the plurality of dosage distribution cabinets (42).
4. The apparatus for preparing mixed denitration agent based on ammonia water + hydrazine as claimed in claim 1, wherein: the preparation device of mixed denitration agent based on aqueous ammonia + hydrazine still include demineralized water storage tank (6), demineralized water is stored in demineralized water storage tank (6), the play liquid end of demineralized water storage tank (6) is connected to hydrazine storage tank (1).
5. The apparatus for preparing mixed denitration agent based on ammonia water + hydrazine as claimed in claim 1, wherein: the hydrazine storage tank (1) is connected with a medicament absorption tank (7).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109758898A (en) * | 2019-02-21 | 2019-05-17 | 上海市机电设计研究院有限公司 | Based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities |
| CN116943415A (en) * | 2023-07-11 | 2023-10-27 | 泊头市境友环保科技有限公司 | Quick dust removal and desulfurization device for flue gas |
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2019
- 2019-02-21 CN CN201920230289.4U patent/CN209828701U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109758898A (en) * | 2019-02-21 | 2019-05-17 | 上海市机电设计研究院有限公司 | Based on ammonium hydroxide+hydrazine mixing denitrfying agent, denitration method for flue gas and preparation facilities |
| CN116943415A (en) * | 2023-07-11 | 2023-10-27 | 泊头市境友环保科技有限公司 | Quick dust removal and desulfurization device for flue gas |
| CN116943415B (en) * | 2023-07-11 | 2024-04-02 | 泊头市境友环保科技有限公司 | Quick dust removal and desulfurization device for flue gas |
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