CN110180348A - A kind of flue gas nitrogen oxide oxidation unit and technique - Google Patents
A kind of flue gas nitrogen oxide oxidation unit and technique Download PDFInfo
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- CN110180348A CN110180348A CN201910523548.7A CN201910523548A CN110180348A CN 110180348 A CN110180348 A CN 110180348A CN 201910523548 A CN201910523548 A CN 201910523548A CN 110180348 A CN110180348 A CN 110180348A
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- flue gas
- oxidizing tower
- tower
- nitrogen oxide
- oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
Abstract
The invention discloses a kind of flue gas nitrogen oxide oxidation units, including oxidizing tower, ozone generator；Oxide isolation entrance is opened up on oxidizing tower, physics adsorption layer is arranged in the fixed bed of oxidizing tower, and oxide isolation entrance is higher than the top of physical absorption layer；The smoke inlet of the oxide isolation entrance of the oxide isolation outlet oxidizing tower of ozone generator, oxidizing tower is connected to flue gas exit pipe road, and the exhanst gas outlet of oxidizing tower is connected to chimney by flue；Also disclose oxidation technology, in conjunction with the advantage and disadvantage of physical absorption enrichment oxidation and ozone oxidation, in the higher region of oxidizing tower inlet flue gas nitrogen oxides using physical absorption enrichment oxidation, a part of NO is oxidized to NO in the case where not consuming oxidant applying and energy consumption2；When NO concentration reduces to a certain extent, further using ozone progress deep oxidation, the NO for being easy to absorb is oxidized to reach and be difficult to the NO that wet absorption removes in nitrogen oxides2, the present invention can realize the high oxidation rate of NO in the case where a small amount of ozone-depleting.
Description
Technical field
The invention belongs to type smoke pollutant removal technical fields, and in particular to a kind of flue gas nitrogen oxide oxidation unit and work
Skill.
Background technique
Contain a large amount of nitrogen oxide NOx in the flue gas that fire coal generates, is to cause one of main reason of atmosphere pollution.Mesh
Before, the NOx in flue gas mainly passes through SCR selective catalytic reduction and is removed, and this method passes through under the effect of the catalyst,
NOx is added into the NH of flue gas3It is reduced into harmless N2, and then remove.Although SCR denitration technology is quite mature at present, according to
It is old that there are problems.Such as catalyst only has greater activity in specific temperature section, and when the adjustment of power plant's operating load, cigarette
The variation of temperature degree can seriously affect SCR denitration efficiency.In addition, there are the secondary pollutions such as the escaping of ammonia, catalyst solid waste for SCR denitration
Problem, and the aging of denitrating catalyst and loss are also quickly, cause operating cost high.In addition to SCR selective reduction
Outside method, also there is wet denitration technology, but requires that the NO gas of indissoluble in NOx is first oxidized to soluble NO2Sour gas, so
Pass through akaline liquid absorbing and removing afterwards.The preposition oxidizing process of common NO has Ozone, peroxide passivation, catalytic oxidation, electro-catalysis
Oxidizing process etc..
Wherein, Ozonation is to react with NO by being mixed into a small amount of ozone gas into flue gas and generate NO2, convenient for adopting
Wet absorption, which is carried out, with lye receives removing.Studies have shown that O3When molar ratio with NO is 1, effect is best, oxidation efficiency
It can be achieved 99% or more.The major defect of Ozonation, which is that ozone is easily decomposes, to be stored, and formed in-situ is needed.Ozone
It is general to produce oxygen ionization by electrion, therefore ozone generator power consumption is higher, unit power consumption is about 10kWh/kg.
It is 500mg/Nm according to NO concentration3Flue gas, 600MW unit need to be equipped with the ozone generator of 1.6t/h, power 16MW.Separately
Outside, the ozone for producing 1kg needs the liquid oxygen of about 10kg, therefore 600MW unit need to consume the liquid oxygen of 16t/h.Power consumption and liquid oxygen
Consumption so that the operating cost of ozone oxidation is higher, can not also promote and apply on a large scale at present.
Summary of the invention
In order to solve problems of the prior art, the present invention provides a kind of flue gas nitrogen oxide oxidation unit and work
Skill, being enriched with oxidation using physical absorption reduces NO concentration, and the NO oxidation technology and method of deep oxidation are then carried out using ozone,
By the way that the consumption of ozone is greatly lowered, realize that Effects Analysis cost reduces 50%-80% or more.
To achieve the goals above, the technical solution adopted by the present invention is that, a kind of flue gas nitrogen oxide oxidation unit, including
Oxidizing tower, ozone generator；Oxide isolation entrance is opened up on oxidizing tower, physics adsorption layer, oxidation is arranged in the fixed bed of oxidizing tower
Medium inlet is higher than the top of physical absorption layer；The oxide isolation of the oxide isolation outlet oxidizing tower of ozone generator enters
Mouthful, the smoke inlet of oxidizing tower is connected to flue gas exit pipe road, and the exhanst gas outlet of oxidizing tower is connected to chimney by flue.
The exit of physical absorption layer is additionally provided with gas injection apparatus, and gas injection apparatus includes several gas injections
Mouthful, the cross section of the jet port covering oxidizing tower, jet port is connected to the oxide isolation entrance on oxidizing tower, gas ejection ports
It is directed downward.
Physical absorption layer is loaded using honeycomb bulk, and physical absorption layer uses ZSM-5 hydrophobic type molecular sieve.
The smoke inlet of the exhanst gas outlet connection oxidizing tower of air-introduced machine is provided on flue gas exit pipe road.
The exhanst gas outlet of air-introduced machine is provided with flowmeter and NO monitoring sensor.
Valve is provided on the outlet conduit of ozone generator.
Oxidizing tower exiting flue gas, which flows to, is arranged spray equipment on the path of chimney；The spray equipment be communicated with for its
Middle input lye or waterpipe；Lye absorption plant and saline solution collecting pit are provided with below the spray equipment.
The spray equipment uses wet-type absorption tower, the smoke inlet of the exhanst gas outlet connection wet-type absorption tower of oxidizing tower；
The top of wet-type absorption tower opens up absorbing liquid entrance, and leakage fluid dram is arranged in the bottom of wet-type absorption tower；Leakage fluid dram is connected to saline solution and collects
The bottom leakage fluid dram in pond, wet-type absorption tower is provided with valve.
Using flue gas nitrogen oxide oxidation unit of the present invention to flue gas nitrogen oxide oxidation technology, flue gas is introduced into oxygen
Change tower, NO is enriched with and aoxidizes in the fixed bed in oxidizing tower, and a part of NO is oxidized to NO by the oxygen fraction in flue gas2；Together
When, oxygen is converted to O under the action of ozone generator3, and the upper end of physical absorption layer in oxidizing tower is inputted, by remaining NO
It is further oxidized to NO2, the nitrogen oxides in oxidizing tower exiting flue gas is with NO2Form output.
From the O of ozone generator input oxidizing tower3Molar ratio with remaining NO is 1:1.
Compared with prior art, the present invention at least has the advantages that
It is higher in oxidizing tower inlet flue gas nitrogen oxides in conjunction with the advantage and disadvantage of physical absorption enrichment oxidation and ozone oxidation
Region is using physical absorption enrichment oxidation, in the case where not consuming oxidant applying and energy consumption by a part in nitrogen oxides
NO is oxidized to NO2.When NO concentration reduces to a certain extent, the method for physical absorption enrichment is difficult in the case where aoxidizing, and use is smelly
Oxygen carries out deep oxidation, is oxidized to the NO for being easy to absorb to reach and be difficult to the NO that wet absorption removes in nitrogen oxides2.This hair
It is bright to realize the high oxidation rate of NO in the case where a small amount of ozone-depleting.
Further, air-introduced machine provides the power into oxidizing tower for flue gas, can effectively overcome flue gas in oxidizing tower and wet
Resistance pressure drop in formula absorption tower.
Further, oxidizing tower exiting flue gas, which flows to, is arranged spray equipment on the path of chimney；The spray equipment connection
Have for inputting lye or waterpipe thereto, flue gas is after the spray equipment, NO2It is converted into diluted acid, nitrate or Asia
The discharge of nitrogen oxides is effectively reduced in nitrate.
Detailed description of the invention
Attached drawing 1 is schematic device of the present invention.
Figure of description is used to provide further understanding of the present invention, and constitutes a part of the invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Specific embodiment
Of the invention to clearly illustrate, below with reference to examples and drawings, the present invention will be described in further detail.Ability
Field technique personnel understand, following the description is not limiting the scope of the invention, it is any make on the basis of the present invention change
Into and variation, all within protection scope of the present invention.
The advantages of physical absorption aoxidizes is that operating cost is low, in addition to overcoming the resistance of activated carbon adsorption layer to need a small amount of power consumption
Outside, substantially without other operating costs.
A kind of flue gas nitrogen oxide oxidation unit, including oxidizing tower 2, ozone generator 3；Oxidation is opened up on oxidizing tower 2 to be situated between
Physics adsorption layer is arranged in matter entrance, the fixed bed of oxidizing tower 2, and oxide isolation entrance is higher than the top of physical absorption layer；Ozone hair
The smoke inlet of the oxide isolation entrance of the oxide isolation outlet oxidizing tower 2 of raw device 3, oxidizing tower 2 is connected to flue gas exit pipe
The exhanst gas outlet in road, oxidizing tower 2 is connected to chimney by flue；
The exit of physical absorption layer is additionally provided with gas injection apparatus, gas injection apparatus in the fixed bed of oxidizing tower 2
Including several gas ejection ports, the cross section of the jet port covering oxidizing tower 2, jet port is connected to the oxidation on oxidizing tower 2 and is situated between
Matter entrance, gas ejection ports are directed downward；The exhanst gas outlet connection oxidizing tower 2 of air-introduced machine 1 is provided on flue gas exit pipe road
Smoke inlet.
The preferred embodiment of the invention, gas injection apparatus use gas distributor, the jet direction of gas injection apparatus
Downward.
The height of gas injection apparatus is adjustable, and gas injection apparatus entrance and oxide isolation entrance are connected by metal hose
It connects.
The exhanst gas outlet of air-introduced machine 1 is provided with flowmeter and NO monitoring sensor.
Valve is provided on the outlet conduit of ozone generator 3；2 exiting flue gas of oxidizing tower flows to be arranged on the path of chimney
Spray equipment；The spray equipment is communicated with for inputting lye or waterpipe thereto；The lower section of the spray equipment is arranged
There are lye absorption plant and saline solution collecting pit.
A preferred embodiment of the present invention, spray equipment use wet-type absorption tower 4, and the exhanst gas outlet of oxidizing tower 2 is connected to
The smoke inlet of wet-type absorption tower 4；The top of wet-type absorption tower 4 opens up absorbing liquid entrance, and row is arranged in the bottom of wet-type absorption tower 4
Liquid mouth；Leakage fluid dram is connected to saline solution collecting pit, and the bottom leakage fluid dram of wet-type absorption tower 4 is provided with valve.
Oxidizing tower 2 is used to aoxidize NO in flue gas, and fixed bed uses active carbon or other physical absorption layers, particle packing or
Gas ejection ports are arranged in the filling of honeycomb bulk, fixed bed upper end；Ozone generator 3 is used to provide NO to oxidizing tower 3 terminal oxidized
O3；Wet-type absorption tower 4 is for absorbing NO2, absorbing liquid is using ammonium hydroxide, NaOH solution or lime stone slurry, wet-type absorption tower 4
Middle setting lye absorption plant.
Device of the present invention is arranged after flue gas ash removal and desulfurization；Flue gas after desulfurization is introduced through air-introduced machine 1 to be aoxidized
Tower 2, NO are enriched on the adsorbent bed in oxidizing tower 2, and a part of NO is oxidized to NO by the oxygen fraction in flue gas2；Meanwhile oxygen
O is converted under the action of ozone generator 33, and the upper end of 2 adsorbent bed of oxidizing tower is inputted, remaining NO is further aoxidized
At NO2, O3Molar ratio with remaining NO is 1:1, and the nitrogen oxides in 2 exiting flue gas of oxidizing tower is mainly with NO2Form it is defeated
Out, it is delivered to wet-type absorption tower 4 to be absorbed, absorbing liquid uses water or lye, correspondingly by NO2It is converted into diluted acid or nitric acid
Salt/nitrite solution discharge.
It is high using ozone oxidation rate, and the consumption of ozone is only related with the total amount of NO, with concentration almost without relationship；
Therefore, by reducing the concentration of entrance NO, the content of NO in flue gas is reduced, the proportional drop of ozone oxidation operating cost may be implemented
It is low；For example, by configuring low NO, by inlet flue gas NOxThe content of middle NO is by 500mg/Nm3It is reduced to 200mg/Nm3,
So, 600MW unit need to only match the ozone generator of 0.64t/h, and operating cost can reduce by 60%.
Physical absorption oxidation oxygenation efficiency is not high, with the reduction of NO concentration and NO in flue gas2The raising of concentration, oxidation rate
Can sharply it decline and finally in NO and NO2Between formed balance.For example, cocoanut active charcoal can be enriched with the NO of oxidation 70-80%, coal
Activated carbon can be enriched with the NO of oxidation 40-50%, and type ZSM 5 molecular sieve can aoxidize the NO of 50-60%.
The present invention increases gas injection apparatus in physical absorption layer exit, by the way that chemical molar equivalent is added in flue gas
Ozone, so that remaining NO is all oxidized to NO2；It is specific: the NO in flue gas being enriched in adsorbent surface, is being partially formed
Higher concentration, to greatly accelerate the oxidation rate of NO, according to kinetics of gas reactions, the oxidation rate of NO and NO's is dense
Degree has following relationship:
Wherein, k is reaction rate constant, related with temperature；[NO2], [NO] and [O2] it is void fraction, unit is
mol/L。
Embodiment 1: by taking 600MW unit as an example, exhaust gas volumn is 2,000,000 mark sides, and the content of NO is 500mg/Nm in flue gas3；
Flue gas is after dedusting and desulfurization, into oxidizing tower 2, ZSM-5 hydrophobic type molecular sieve is filled in oxidizing tower 2, for the resistance for reducing flue gas
Power loss, and prevent a small amount of dust after desulfurization from generating blocking to molecular sieve, system with molecular sieve for preparing is at honeycomb bulk；ZSM-5 hydrophobic type
Molecular sieve under conditions of wet flue gas is 50% to the adsorption and oxidation rate of NO after desulfurization, is remained in the flue gas after adsorbent bed adsorption and oxidation
The concentration of remaining NO is 250mg/Nm3, the yield of ozone of ozone generator 3 is 0.8t/h, and power 8MW, liquid oxygen consumption is 8t/
The final oxygenation efficiency of h, NO is 99%, and NO content is 5mg/Nm in 2 exiting flue gas of oxidizing tower3, NO is absorbed by wet-type absorption tower 42
Afterwards, NO in neat stressxContent is 5mg/Nm3。
Embodiment 2: by taking the 600MW unit for configuring low NO as an example, exhaust gas volumn is 2,000,000 mark sides, NO in flue gas
Content is 200mg/Nm3。
Process flow is same as Example 1, and NO content is 100mg/ in the flue gas after 2 adsorbent bed adsorption and oxidation of oxidizing tower
Nm3；The yield of ozone of ozone generator 3 is 0.32t/h, and power 3.2MW, liquid oxygen consumption is 3.2t/h, and NO is finally aoxidized
Rate is 99%, NO in the neat stress that wet-type absorption tower 4 is dischargedxContent is 5mg/Nm3。
Comparative example: comparative example uses tradition NO ozone-oxidizing device, Gas Parameters and the phase in embodiment 1
Together；For the NO oxidation for realizing 99%, the yield of ozone of ozone generator 3 is 1.6t/h, power 16MW, and liquid oxygen consumption is
16t/h absorbs NO through wet-type absorption tower2NOx content is 5mg/Nm in neat stress afterwards3。
Table 1 is compared using the embodiment 1,2 of apparatus of the present invention and the consumption indicators of comparative example
Note: ozone production power consumption takes 10kWh/kg, and liquid oxygen yield of ozone takes 10%.
As known from the above, ozone-depleting 50% can be reduced using NO oxidation unit of the present invention, and then reduces operation electricity
Consumption and liquid oxygen consumption each 50%；Apparatus of the present invention are used on the basis of configuring low NO, can install every MW equivalent
The ozone consumption of flue gas is down to 0.53kg/h by 2.67kg/h, and ozone generator station service power consumption rate is down to 0.53% by 2.67%；
Operating cost decline is significant, has good popularization and application foreground.
Claims (10)
1. a kind of flue gas nitrogen oxide oxidation unit, which is characterized in that including oxidizing tower (2), ozone generator (3)；Oxidizing tower
(2) oxide isolation entrance is opened up on, physics adsorption layer is arranged in the fixed bed of oxidizing tower (2), and oxide isolation entrance is inhaled higher than physics
The top of attached layer；The oxide isolation entrance of the oxide isolation outlet oxidizing tower (2) of ozone generator (3), oxidizing tower (2)
Smoke inlet is connected to flue gas exit pipe road, and the exhanst gas outlet of oxidizing tower (2) is connected to chimney by flue.
2. flue gas nitrogen oxide oxidation unit according to claim 1, which is characterized in that the exit of physical absorption layer is also
It is provided with gas injection apparatus, gas injection apparatus includes several gas ejection ports, the cross of jet port covering oxidizing tower (2)
Section, jet port are connected to the oxide isolation entrance on oxidizing tower (2), and gas ejection ports are directed downward.
3. flue gas nitrogen oxide oxidation unit according to claim 2, which is characterized in that physical absorption layer uses honeycomb block
Shape filling, physical absorption layer use ZSM-5 hydrophobic type molecular sieve.
4. flue gas nitrogen oxide oxidation unit according to claim 1, which is characterized in that flue gas exit pipe is provided on road
The smoke inlet of exhanst gas outlet connection oxidizing tower (2) of air-introduced machine (1).
5. flue gas nitrogen oxide oxidation unit according to claim 4, which is characterized in that the exhanst gas outlet of air-introduced machine (1)
It is provided with flowmeter and NO monitoring sensor.
6. flue gas nitrogen oxide oxidation unit according to claim 5, which is characterized in that the outlet of ozone generator (3)
Valve is provided on pipeline.
7. flue gas nitrogen oxide oxidation unit according to claim 1, which is characterized in that oxidizing tower (2) exiting flue gas stream
Spray equipment is set on the path of chimney；The spray equipment is communicated with for inputting lye or waterpipe thereto；It is described
Lye absorption plant and saline solution collecting pit are provided with below spray equipment.
8. flue gas nitrogen oxide oxidation unit according to claim 7, which is characterized in that the spray equipment uses wet type
Absorption tower (4), the smoke inlet of exhanst gas outlet connection wet-type absorption tower (4) of oxidizing tower (2)；The top of wet-type absorption tower (4)
Absorbing liquid entrance is opened up, leakage fluid dram is arranged in the bottom of wet-type absorption tower (4)；Leakage fluid dram is connected to saline solution collecting pit, wet-type absorption tower
(4) bottom leakage fluid dram is provided with valve.
9. using flue gas nitrogen oxide oxidation unit described in claim 1 to flue gas nitrogen oxide oxidation technology, which is characterized in that
Flue gas is introduced into oxidizing tower (2), and NO is enriched with and aoxidizes in the fixed bed in oxidizing tower (2), and a part of NO is by the oxygen in flue gas
Gas partial oxidation is at NO2；Meanwhile oxygen is converted to O under the action of ozone generator (3)3, and input the suction of oxidizing tower (2) physics
Remaining NO is further oxidized to NO by the upper end of attached layer2, the nitrogen oxides in oxidizing tower (2) exiting flue gas is with NO2Form
Output.
10. flue gas nitrogen oxide oxidation technology according to claim 9, which is characterized in that inputted from ozone generator (3)
The O of oxidizing tower (2)3Molar ratio with remaining NO is 1:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112774412A (en) * | 2020-12-17 | 2021-05-11 | 国网河北省电力有限公司电力科学研究院 | Flue gas treatment device |
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Cited By (1)
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