CN110102160A - The low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction - Google Patents
The low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction Download PDFInfo
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- CN110102160A CN110102160A CN201910431173.1A CN201910431173A CN110102160A CN 110102160 A CN110102160 A CN 110102160A CN 201910431173 A CN201910431173 A CN 201910431173A CN 110102160 A CN110102160 A CN 110102160A
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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
- B01D53/46—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
- B01D53/75—Multi-step processes
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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
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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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
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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
- B01D2251/106—Peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a kind of low-temperature denitration methods of hydrogen peroxide oxidation combination selective catalytic reduction, comprising the following steps: 1) for the boiler smoke after dedusting, sprays into hydrogen peroxide and carry out SCR denitration reaction by spraying；2) nitrogen dioxide generated by spraying by spraying into hydrogen peroxide recycles selective catalytic reduction (SCR) to carry out denitration, the decomposition and raising low-temperature denitration reaction rate of the ammonium hydrogen sulfate on accelerator activator surface.This method reaches both without consumption energy, improves SCR reactivity, in turn avoids the integrated effect of catalyst poisoning phenomenon.
Description
Technical field
The invention belongs to flue gas pollutant Treatment process fields more particularly to a kind of hydrogen peroxide oxidation to urge in conjunction with selectivity
Change the efficient cryogenic method of denitration of reduction method (SCR).
Background technique
With the more sternness of atmosphere pollution, standard limit of smog release is increasingly strict, and 2016, country proposed stringent surpass
Low emission standard, by coal fired power plant nitrogen oxides 100mg/m3Discharge limitation be reduced to 50mg/m3.Selective catalytic reduction
Method (SCR) is method of denitration commonly used at present, and SCR method denitration efficiency is high, and secondary pollution is lower, but this is only limitted to high temperature
In the case where flue gas, the SCR method in low-temperature flue gas still has shortcoming, wherein primary disadvantage is that in low temperature condition
Under SCR reactivity it is lower, in addition there are SO in most flue gasx, SOxVery easy and NH at low temperature3Reaction generates
Ammonium sulfate is attached to catalyst surface, leads to catalyst inactivation, seriously affects denitrating flue gas efficiency, at present under low temperature condition
NOxRemoving, generally use and low-temperature flue gas be heated to high temperature, then use SCR denitration technology, but this technology will be additional
The heating of secondary energy sources is needed, this will make this technology add more equipment, increase operating cost.
It is referred in the Chinese patent of Publication No. CN107606629A a kind of by gasification heating device prevention hydrogen sulfate
The denitration technology of ammonium blocking, this denitration technology require the equipment used very much, need the heating of secondary energy sources, consume a large amount of energy
Amount, increases operating cost.
A kind of catalysis of support type low temperature sulfuric-resisting hydrogen ammonium is referred in the Chinese patent of Publication No. CN107497465A
Agent technology of preparing, although using this optimization catalyst it is possible to prevente effectively from catalyst inactivation phenomenon, it is anti-can not to improve SCR
The activity answered.
Therefore developing one kind can not need additionally to consume energy, to avoid sulfur poisoning phenomenon and can improve SCR reaction work
The method for oxidizing and denitrating of three kinds of advantages of property, can greatly promote the industrial application process of denitration technology.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of low in cost, denitration efficiencies
The low-temperature denitration method of high hydrogen peroxide oxidation combination selective catalytic reduction (SCR).
The low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction, includes the following steps:
1) it for the boiler smoke after dedusting, sprays into hydrogen peroxide and carries out SCR denitration reaction by spraying；
2) nitrogen dioxide generated by spraying by spraying into hydrogen peroxide, recycles selective catalytic reduction (SCR) to carry out
Denitration, the decomposition and raising low-temperature denitration reaction rate of the ammonium hydrogen sulfate on accelerator activator surface；Reach both without consuming energy,
SCR reactivity is improved, the integrated effect of catalyst poisoning phenomenon is in turn avoided.
As a preferred solution of the present invention, the temperature of the boiler smoke after the dedusting is 150-280 DEG C, dust-laden
Amount is lower than 100mg/m3；Step is handled as follows
1) hydrogen peroxide gas is sprayed into, i.e. penetrating oxidant；
Hydrogen peroxide gas is decomposed reaction immediately, and largely free OH is dispersed in flue gas and an oxidation at this time
Nitrogen, which combines, generates nitrogen dioxide.Reaction equation is as follows:
H2O2→2·OH (1)
2·OH+NO→NO2+H2 (2)
2) Fast SCR reacts
NO+NO2+2NH3→2N2+3H2O (3)
It is made of Fast SCR the nitrogen dioxide combination nitric oxide and ammonia generated in (2) formula, nitrogen dioxide can be
Ammonium hydrogen sulfate under low temperature on accelerator activator surface decomposes, avoid occurring catalyst inactivation phenomenon, and nitrogen dioxide is deposited
High denitration efficiency is being obtained at low temperature.
As another preferred embodiment of the invention, the spray dosage of the hydrogenperoxide steam generator is hydrogen peroxide and an oxygen
The molar ratio for changing nitrogen is 1:1-1:20；The mass percent concentration of the hydrogenperoxide steam generator is 0.5%-50%.
As an improvement of the present invention, the mass percent concentration of oxygen is 5%-15% in flue gas.
As another improvement project of the invention, the gaseous oxidation temperature is at 150-280 DEG C.
As a further improvement of the present invention, catalysis reduction part is all made of the V of low vanadium load2O5-WO3/
TiO2Catalyst, wherein V2O5Load capacity 0.1wt%-5wt%, WO3Load capacity 1wt%-10wt%.
As further improvement project of the invention, the nitric oxide concentration and concentration of hydrogen peroxide ratio are 1:1-1:
20。
Relative to current denitration technology, the present invention provides a kind of hydrogen peroxide oxidation combination selective catalytic reduction
(SCR) low-temperature denitration method, the characteristic of this method are Hydrogen Peroxide Pre-Oxidation nitric oxide, first can will be in flue gas
Nitric oxide partial oxidation generates nitrogen dioxide, and in addition catalyst reduction layer uses the V of low vanadium load2O5-WO3/TiO2Catalysis
Agent, the deposition of ammonium sulfate will not be influenced and be generated by sulfur dioxide by obtaining the type catalyst substantially by experiment, but low
Denitration activity is lower in warm situation, and in the presence of nitrogen dioxide, nitric oxide, nitrogen dioxide is constituted on catalyst surface
The reaction mechanism of Fast SCR, both can the ammonium hydrogen sulfate at low temperature on accelerator activator surface decompose, avoid urging
Agent deactivation phenomenom, the presence of another aspect nitric oxide, nitrogen dioxide obtain high denitration efficiency at low temperature, improve reaction
Activity, and the heating device at present in low-temperature denitration can be saved, method of denitration can be made to run under low temperature, low energy consumption,
Investment and operating cost are saved, economic benefit is improved.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the present invention.
Fig. 2 is the schematic diagram for the oxidation reaction combination Fast SCR reaction unit that the embodiment of the present invention uses, in which: 1, flue gas
Entrance；2, hydrogen peroxide spray head；3, ammonia-gas spraying device；4, it is catalyzed reduction zone；5, exhanst gas outlet.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.
The low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction, method flow as shown in Figure 1, using
Oxidation reaction combination Fast SCR reaction unit as shown in Figure 2 implements this method, and oxidation reaction apparatus material uses acid and alkali-resistance
Oxidation resistant stainless steel material, the flue gas after dedusting enter from the smoke inlet 1 of reaction unit, and hydrogen peroxide gas passes through spray head
2 spray into flue, and by ammonia-gas spraying device 3, and then in catalysis reduction zone 4 Fast SCR reaction occurs for the flue gas after reaction, after denitration
Flue gas by exhanst gas outlet 5 be discharged flue；Method includes the following steps:
1) it for the boiler smoke after dedusting, sprays into hydrogen peroxide and carries out SCR denitration reaction by spraying；
2) nitrogen dioxide generated by spraying by spraying into hydrogen peroxide, recycles selective catalytic reduction (SCR) to carry out
Denitration, the decomposition and raising low-temperature denitration reaction rate of the ammonium hydrogen sulfate on accelerator activator surface.
Embodiment 1
Denitrating flue gas process is simulated on experiment simulator.Exhaust gas volumn 1L/min, flue gas composition are as follows: O2For 5%, NO
For 500pm, remaining is nitrogen, and 200 DEG C of flue-gas temperature, pressure is an atmospheric pressure.150 μ of injection rate of hydrogen peroxide gas
L/min, wherein hydrogenperoxide steam generator mass percent is 30%, and the removal efficiency of nitrogen oxides can promote 30%~60%.
Embodiment 2
Denitrating flue gas process is simulated on experiment simulator.Exhaust gas volumn 1L/min, flue gas composition are as follows: O2For 5%, NO
For 500pm, remaining is nitrogen, and 250 DEG C of flue-gas temperature, pressure is an atmospheric pressure.200 μ of injection rate of hydrogen peroxide gas
L/min, wherein hydrogenperoxide steam generator mass percent is 30%, and the removal efficiency of nitrogen oxides can promote 30%~80%.
Embodiment 3
Denitrification process on experiment simulator after simulated flue gas sulphation.It is passed through SO2For 500ppm, 250 DEG C of maintenances
1.5h.Exhaust gas volumn 1L/min, flue gas composition are as follows: O2For 5%, NO 500pm, remaining is nitrogen, 250 DEG C of flue-gas temperature, is pressed
Power is an atmospheric pressure.The 200 μ l/min of injection rate of hydrogen peroxide gas, wherein hydrogenperoxide steam generator mass percent be
30%, the removal efficiency of nitrogen oxides can promote 30%~80%, illustrate that hydrogen peroxide oxidation of the invention is urged in conjunction with selectivity
The low-temperature denitration method for changing reduction method (SCR) has high antisulphuric ability at 250 DEG C.
Embodiment 4
Denitrification process on experiment simulator after simulated flue gas sulphation.It is passed through SO2For 500ppm, 200 DEG C of maintenances
1.5h.Exhaust gas volumn 1L/min, flue gas composition are as follows: O2For 5%, NO 500pm, remaining is nitrogen, 200 DEG C of flue-gas temperature, is pressed
Power is an atmospheric pressure.The 60 μ l/min of injection rate of hydrogen peroxide gas, wherein hydrogenperoxide steam generator mass percent be
30%, the removal efficiency of nitrogen oxides can promote 20%~60%, illustrate that hydrogen peroxide oxidation of the invention is urged in conjunction with selectivity
The efficient cryogenic method of denitration for changing reduction method (SCR) has high antisulphuric ability at 200 DEG C.
Embodiment 5:
Denitrating flue gas process is simulated on experiment simulator.Exhaust gas volumn 1L/min, flue gas composition are as follows: O2For 5%, NO
For 500pm, remaining is nitrogen, and 200 DEG C of flue-gas temperature, pressure is an atmospheric pressure.The 80 μ l/ of injection rate of hydrogen peroxide gas
Min, wherein hydrogenperoxide steam generator mass percent is 30%, and the removal efficiency of nitrogen oxides can promote 20%~60%.
It illustrates, the above case is only preferable case study on implementation of the invention, and the present invention can also be in the above method
Concrete operation step and various reactants are replaced.Therefore it is all with equivalent made by specification and diagramatic content of the invention
Variation is directly or indirectly applied in other correlative technology fields and is both contained in the range of of the invention cover.
Claims (8)
1. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction, which comprises the following steps:
1) it for the boiler smoke after dedusting, sprays into hydrogen peroxide and carries out SCR denitration reaction by spraying；
2) nitrogen dioxide generated by spraying by spraying into hydrogen peroxide, recycles selective catalytic reduction (SCR) to carry out denitration,
The decomposition and raising low-temperature denitration reaction rate of the ammonium hydrogen sulfate on accelerator activator surface.
2. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the temperature of the boiler smoke after the dedusting is 150-280 DEG C, and dustiness is lower than 100mg/m3。
3. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the spray dosage of the hydrogenperoxide steam generator is hydrogen peroxide and nitric oxide production molar ratio is 1:1-1:20.
4. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the mass percent concentration of the hydrogenperoxide steam generator is 0.5%-50%.
5. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the mass percent concentration of oxygen is 5%-15% in flue gas.
6. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the gaseous oxidation temperature is at 150-280 DEG C.
7. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: catalysis reduction part is all made of the V of low vanadium load2O5-WO3/TiO2Catalyst, wherein V2O5Load capacity 0.1wt%-
5wt%, WO3Load capacity 1wt%-10wt%.
8. the low-temperature denitration method of hydrogen peroxide oxidation combination selective catalytic reduction according to claim 1, special
Sign is: the nitric oxide concentration is 1:1-1:20 with concentration of hydrogen peroxide ratio.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999635A (en) * | 2019-04-30 | 2019-07-12 | 山东默锐环境产业股份有限公司 | NO in a kind of boiler smokeXSome redox removal methods and removing means |
| CN111298642A (en) * | 2020-02-26 | 2020-06-19 | 郑州大学 | Method and device for denitration by low-temperature flue gas section free radical enhanced selective catalytic reduction |
| CN111346509A (en) * | 2020-04-28 | 2020-06-30 | 苏州西热节能环保技术有限公司 | Diagnosis method for ammonium bisulfate poisoning of SCR denitration catalyst |
| CN112742211A (en) * | 2019-10-30 | 2021-05-04 | W.L.戈尔及同仁股份有限公司 | Improving the catalytic efficiency of flue gas filtration |
| CN113750783A (en) * | 2021-08-24 | 2021-12-07 | 福建华电可门发电有限公司 | Method of two-section type SCR reaction device suitable for wide-temperature-zone denitration |
| CN115253671A (en) * | 2022-08-13 | 2022-11-01 | 嘉兴复翼环保科技有限公司 | NO capable of assisting power by utilizing 2 Method for realizing SCR (selective catalytic reduction) efficient denitration by using generated additive |
| US11602717B2 (en) | 2019-10-30 | 2023-03-14 | W. L. Gore & Associates, Inc. | Catalytic efficiency of flue gas filtration |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999635A (en) * | 2019-04-30 | 2019-07-12 | 山东默锐环境产业股份有限公司 | NO in a kind of boiler smokeXSome redox removal methods and removing means |
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| CN111346509A (en) * | 2020-04-28 | 2020-06-30 | 苏州西热节能环保技术有限公司 | Diagnosis method for ammonium bisulfate poisoning of SCR denitration catalyst |
| CN113750783A (en) * | 2021-08-24 | 2021-12-07 | 福建华电可门发电有限公司 | Method of two-section type SCR reaction device suitable for wide-temperature-zone denitration |
| CN115253671A (en) * | 2022-08-13 | 2022-11-01 | 嘉兴复翼环保科技有限公司 | NO capable of assisting power by utilizing 2 Method for realizing SCR (selective catalytic reduction) efficient denitration by using generated additive |
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Application publication date: 20190809 |