CN107215854A - A kind of devices and methods therefor for producing nitric acid - Google Patents
A kind of devices and methods therefor for producing nitric acid Download PDFInfo
- Publication number
- CN107215854A CN107215854A CN201710172151.9A CN201710172151A CN107215854A CN 107215854 A CN107215854 A CN 107215854A CN 201710172151 A CN201710172151 A CN 201710172151A CN 107215854 A CN107215854 A CN 107215854A
- Authority
- CN
- China
- Prior art keywords
- nitric acid
- absorbing cabin
- active oxygen
- absorbing
- cabin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/40—Preparation by absorption of oxides of nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
The present invention relates to one kind without HTHP and catalyst, using the gaseous nitrogen oxide or gaseous state hydronitrogen of separate sources, the apparatus and method that dust technology is produced even with industrial waste gas.In this method, gaseous nitrogen oxide or gaseous state hydronitrogen excited oxygen atom O (1D), under active oxygen radical (ROS), with the hydroxyl radical free radical synergy in absorbing cabin, the nitrogen oxides of generation high-valence state is oxidized, then nitric acid is converted into by absorbing cabin.
Description
(1) technical field：
The present invention relates to the method and its device that a kind of utilization gas phase nitrogen oxides or gaseous state hydronitrogen prepare nitric acid,
More particularly to a kind of method without preparing nitric acid under conditions of HTHP and catalyst.
(2) background technology：
Nitric acid is as a kind of one of important chemical products, and it is catalyzed in agricultural, army's industry, chemical industry, the neck such as organic synthesis
Domain has a wide range of applications value.And the very cumbersome (figure of conventional method (ammonia catalytic oxidation) process equipment for preparing nitric acid
1), i.e., ammonia reacts generation nitric oxide at high temperature with the oxygen in air, and nitric oxide is further generated by catalysis oxidation
Nitrogen dioxide, nitrogen dioxide is only absorbed by the water generation nitric acid, and the nitric acid of various concentrations is generated finally by distillation.During the course of the reaction
HTHP is needed, and needs noble metal as catalyst.
During nitric acid is produced, ammonia, it is necessary to be first oxidized to nitric oxide, nitrogen dioxide, then is joined as nitrogen source
With follow-up oxidation reaction, so nitrogen oxides or ammonia are the necessary raw materials for producing nitric acid, and in the industrial production, some works
Contain substantial amounts of nitrogen oxides or hydronitrogen (ammonia, hydrazine etc.) in the gas that factory is discharged, nitrogen oxides is that air is dirty
One of major pollutants of dye, country discharges strict standard to it, and regard the nitrogen oxides in gas phase as production nitre
The nitrogen source of acid be can yet be regarded as a kind of method of innovation, both can be with purifying harmful gas, again can profit using nitrogen oxides as one kind
Resource.It produces the process of nitric acid without HTHP and catalyst, and the income that nitric acid is brought can also save industry
The operating cost of environmental protection equipment.At present, it is that nitrogen source mainly has following to produce the technology of nitric acid using the nitrogen oxides in gas phase
Several, one prepares nitric acid (patent No. CN204193769U) to be absorbed using the scheme of multistage back washing, the technology production equipment
It is excessively complicated, and it is only applicable to the higher gas of nitrous oxides concentration.Two be to containing nitrogen oxides using ozone or hydrogen peroxide
Gas aoxidized, and reclaim nitric acid (patent No. CN204380494U) using water or nitric acid as absorbent, this technical matters
Equipment is simple but to the larger high expensive of demand of oxidant, and oxidation efficiency is not high.Operating cost is determined in industrial use
Determine economic feasibility, therefore how to reduce the emphasis that operating cost should be research and development.Three be to use adsorbent by nitrogen oxides
It is aoxidized with oxidant after enrichment, desorption, the last aqueous solution absorbs relieving haperacidity (patent No. CN204824173U).This technology not by
The influence of nitrous oxides concentration in gas phase, but its complex process, and adsorbent heteropoly acid is expensive and service life is not long.
(3) content of the invention：
There is not paired electronics on nitric oxide production nitrogen-atoms, molecular polarity is small, and this makes itself and other nitrogen oxides
It is poor compared to water solubility.In method involved in the present invention, the lower valency such as nitric oxide nitrogen oxides can turn at low temperature
It is changed into nitrogen dioxide and the nitrogen oxides of other high-valence states, and is only absorbed by the water generation nitric acid.
The production of nitric acid can be divided into the three below stage in the present invention：
First stage：Active oxygen radical is formed in active oxygen radical generator, and (active oxygen radical includes exciting
State oxygen atom O (1D), free radical of the hydroxyl radical free radical etc. containing oxygen atom), and be input in airflow line；Active oxygen is free
The position of base generator needs careful selection, so that ROS can be sufficiently mixed with nitrogen oxides or gaseous state hydronitrogen air-flow.
The ROS of generation need to be contacted with the nitrogen oxides in gas phase or gaseous state hydronitrogen in 0.1 second.
In the present invention active oxygen radical generator can using photodissociation be catalyzed storehouse come photodissociation ozone (or electrolytic catalysis storehouse electricity
Solve ozone), ozone is to be produced by ozone generator with the air of compression, and the ozone amount produced as needed is smelly to adjust
The power of Oxygen Generator, the present invention only needs to produce low concentration ozone, this and single do the technology phase of oxidant using a large amount of ozone
It is more worthwhile than more economical.
1. ozone is the allotrope of oxygen, chemical property is very unstable, and its UV Absorption wave-length coverage is 220
~350nm.
2. when ultra violet lamp ozone, can produce immediately excited oxygen atom O (1D), this reaction has higher reaction
Activity.
3. excited oxygen atom O (1D other active oxygen radicals, such as hydroxyl will be generated by) being contacted with moisture in air
Base free radical, so as to trigger the chain reaction of free radical.
4. moisture in air can generate active oxygen radical, such as hydroxyl under ultraviolet light (220~350nm of wavelength) irradiation
Free radical.
Chemical equation：
Second stage：Gas containing gaseous nitrogen oxide or gaseous state hydronitrogen flows in airflow line, gaseous state
Gas phase oxidation process occurs for nitrogen oxides or gaseous state hydronitrogen, and product is passed through absorbing cabin；In this stage nitric oxide
(NO) lower valency nitrogen oxides or gaseous state hydronitrogen based on are converted to the nitrogen oxides of more expensive state, such as：Titanium dioxide
Nitrogen (NO2), nitrogen trioxide (N2O3), dinitrogen pentoxide (N2O5), nitrous acid (HNO2) etc..After the NO_x formation of high-valence state
It must avoid by ultra violet lamp, because this can trigger back reaction；The reaction speed of back reaction is very fast, can make high price moment
State nitrogen oxides becomes nitric oxide again.
Nitrogen oxides in airflow line can be used exclusively for manufacture nitric acid contain gaseous nitrogen oxide or gaseous nitrogen
The gas of hydrogen compound (such as ammonia) or the industrial waste gas containing gaseous nitrogen oxide or gaseous state hydronitrogen.Such as
Fruit uses industrial waste gas, and the present apparatus and method can play a part of purifying waste gas simultaneously.
Phase III：In absorbing cabin nitric acid is generated using liquid absorption gaseous nitrogen oxide.
Absorbing cabin
1. absorbent solution includes：Water, nitric acid and hydrogen peroxide.
2. the pH value of absorbent solution is needed with nitric acid regulation to 2~4, it should not be adjusted with other acids, in order to avoid impurity is introduced,
The concentration of nitric acid is no more than 6mol/L in the absorbing cabin.
It is optimal that 3. the hydrogen peroxide concentration in absorbing cabin need to be maintained at 150~250mmol/L.
4. the high-valence state oxynitrides formed in photodissociation catalysis storehouse needs to contact most preferably with absorbing liquid in 0.1 second.
Unsuitable and ultraviolet light exposure after 5. the high-valence state oxynitrides of photodissociation catalysis generation is formed.
6. the high-valence state oxides of nitrogen gas of photodissociation catalysis generation, need to be directed to be passed through in absorbing liquid most preferably in 0.1 second.
7. the component of absorbing cabin and absorbing liquid is all in accordance with patent CN201410166820.8 and CN201410166764.8
It is designed to implement.
8. for guarantee yield, the time of contact of the high-valence state nitrogen oxides of absorbing liquid and gas phase need to be more than 1 second.
9. to ensure yield, the residence time need to be more than 1 second in absorbing cabin for the high-valence state nitrogen oxides of gas phase.
10. the ozone not being catalyzed by photodissociation also can absorbed liquid solution absorption.
11. the optimum temperature range of absorbing liquid is more than 0 DEG C, less than or equal to 50 DEG C.
12. by the Stress control of absorbing cabin in certain scope, to promote high-valence state nitrogen oxides more preferable
Absorb.
13. the preferred pressure for absorbing high-valence state oxynitrides is 2~6KPa.
Chemical equation：
NO+O·→NO2·
NO2·+NO→N2O3·
N2O3·+2HO·+O2→2HNO3+O·
NO2+O·→NO3·
NO3·+NO2·→N2O5
N2O5+H2O→2HNO3
NO2·+HO·→HNO3
3NO2·+H2O→2HNO3+NO·
NO·+H2O2→HNO3+H·
Technical scheme：
Scheme 1, a kind of device for producing nitric acid, it is characterised in that：
Its structure includes an active oxygen radical generator, an airflow line and an absorbing cabin；Wherein active oxygen
Free-radical generator has gas outlet；Absorbing cabin has an absorbing cabin air inlet, absorbing cabin gas outlet, dosing mouth, discharging opening, active oxygen from
Airflow line is passed through by the gas outlet of base generator, airflow line is passed through below absorbing cabin liquid levels from absorbing cabin air inlet.
The device of scheme 2, a kind of production nitric acid as described in scheme 1, it is characterised in that：
The active oxygen radical generator is a photodissociation catalysis storehouse；Wherein photodissociation catalysis storehouse includes uviol lamp, purple
Outer light must not be irradiated in airflow line.
The device of scheme 3, a kind of production nitric acid as described in scheme 1, it is characterised in that：The wavelength of uviol lamp be 220~
350nm。
The device of scheme 4, a kind of production nitric acid as described in scheme 1, it is characterised in that：
The gas outlet in photodissociation catalysis storehouse is located at airflow line close at absorbing cabin air inlet.
The device of scheme 5, a kind of production nitric acid as described in scheme 1, it is characterised in that：There is undersaturated nitre in absorbing cabin
Acid solution and hydrogen peroxide solution.
The device of scheme 6, a kind of production nitric acid as described in scheme 1, it is characterised in that：
There are pressure valve and pressure sensor in absorbing cabin.
The device of scheme 7, a kind of production nitric acid as described in scheme 1, it is characterised in that：There is TEMP in absorbing cabin
Device.
Scheme 8, a kind of method for producing nitric acid, it is characterised in that：
The production of nitric acid can be divided into the three below stage：
First stage：Active oxygen radical is formed in active oxygen radical generator, and is input in airflow line；
Second stage：Gas phase oxidation process occurs for nitrogen oxides or gaseous state hydronitrogen in airflow line, and product leads to
Enter absorbing cabin；
Phase III：In absorbing cabin nitric acid is generated using liquid absorption gaseous nitrogen oxide.
Scheme 9, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：
First stage：Active oxygen radical generator is a photodissociation catalysis storehouse, wherein using ozone formation active oxygen certainly
By base.
Scheme 10, a kind of method for producing nitric acid as described in scheme 9, it is characterised in that：
The first stage：
(1) ozone is produced using compressed air, and Ozone transfer to photodissociation is catalyzed storehouse；
(2) ozone photodissociation is catalyzed into excited oxygen atom using uviol lamp in photodissociation catalysis storehouse；
(3) excited oxygen atom reacts to form active oxygen radical with vapor, triggers the chain reaction of free radical；Scheme
11st, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：
The second stage：
(1) ozone gas comprising active oxygen radical of generation is passed through in airflow line, in described airflow line
Ultraviolet light should have been avoided；
(2) active oxygen radical is sufficiently mixed with nitrogen oxides or gaseous state hydronitrogen air-flow, in gas phase reaction, gas
State nitrogen oxides reacts with active oxygen radical, so as to form the oxynitrides of more expensive state；
Scheme 12, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：
The phase III：
(1) the oxynitrides mixed gas for the more expensive state for forming second stage is passed through absorbing cabin, utilizes unsaturation
Salpeter solution absorb；
(2) oxidant hydrogen peroxide is added in cabin is absorbed, with the ozone one of not participating in reaction of the part from photodissociation storehouse
Rise and provide oxidation environment for the solution in absorbing cabin；
(3) nitrogen oxides of high-valence state is converted generation nitric acid in absorbing liquid.
Scheme 13, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：Work will be included described in generation
The ozone gas of property oxygen radical was passed through in airflow line in 0.1 second.
Scheme 14, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：The consumption of the ozone and institute
The mol ratio of the nitrogen oxides of aerobicization is 0.3~1.0.
Scheme 15, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：Dioxygen in the absorbing cabin
Water concentration need to be maintained at 150~250mmol/L.
A kind of method that produces nitric acid of the scheme 16. as described in scheme 8, it is characterised in that：Nitric acid in the absorbing cabin
Concentration is no more than 6mol/L.
A kind of method that produces nitric acid of the scheme 17. as described in scheme 8, it is characterised in that：Described high-valence state nitrogen oxidation
Compound needs to contact with absorbing liquid in 0.1 second.
Scheme 18, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：The high-valence state of described gas phase
Nitrogen oxides residence time in absorbing cabin is more than or equal to 1 second.
Scheme 19, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：The temperature of described absorbing liquid
Scope is to be less than or equal to 50 DEG C more than 0 DEG C.
Scheme 20, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：The pressure control of the absorbing cabin
System is in 2~6KPa.
Scheme 21, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：The absorbing cabin nitric acid is water-soluble
The pH value of liquid is 2~4.
Scheme 22, a kind of method for producing nitric acid as described in scheme 8, it is characterised in that：It is described to contain gaseous state nitrogen oxidation
The gas of thing is the industrial waste gas containing gaseous nitrogen oxide or gaseous state hydronitrogen.
The superiority of the present invention：
Process involved in the present invention can utilize nitrogen oxides or gaseous nitrogen in gas phase under low temperature and low pressure
Hydrogen compound produces dust technology.In this technical scheme, the light of nitrogen oxides or gaseous state hydronitrogen in gas phase in ozone
The nitrogen oxides of high-valence state is generated under the synergy of solution catalysis and catalytic oxidation of hydrogen peroxide, nitre is finally absorbed to generate
Acid.The technical matters equipment is simple, and cost of material is low, it is easy to promote, and economic feasibility is high in industrial use, available for industry
Exhaust-gas treatment, it is adaptable to coal burning and gas burning boiler, and ensure that the discharge of nitrogen oxides of exhaust gas is less than national standard.
(4) illustrate：
Fig. 1:The conventional method of nitric acid is prepared, process and equipment are very cumbersome (data source is in U.S. BASF)
Fig. 2：The generation of oxygen radical and injected system
201. active oxygen radical generators (can be a photodissociation catalysis storehouse)
The active oxygen radical gas outlet of 202. ozone inlet 203.
The denitrating system of 204. airflow line, 205. platform 206. is pointed to
207. gas nitrogen oxides or gaseous state hydronitrogen flow direction
Fig. 3：Oxygen radical generator interior views
The flanged quartz socket tube of 301. uviol lamp 302.
Fig. 4：Active oxygen radical generator external view
401. flanges lock quartz socket tube
Fig. 5 seals locking system detail drawing
501. sealing locking silica gel pad a 502. seal the quartz flanges of locking silica gel pad b 503.
The ultraviolet lamp sleeves of 504. steel flange system a, 505. steel flange system b 506.
Fig. 6 ozone generator top end view detail drawings
Fig. 7 absorbing cabin front views
The auxiliary entrance of 701. pressure valve, 702. demister, 703. water inlet 704. (in water filling port, the connection such as dosing mouth
, can manually dosing when automated system breaks down)
The main cabin doors of 705. electronic liquid level sensor a, 706. electronic liquid level sensor b 707.
708. customization multijaw pipelines (including 1 main pipeline and multiple bypass ducts, it is ensured that gas-liquid mixed is abundant)
709. custom cuts mouthful (for gas-liquid mixed and reducing back pressure)
The discharging opening of 710. temperature sensor, 711. sample tap 712.
The dosing mouth of 713. draining valve, 714. fluid level indicator 715.
The gas outlet of 716. hydrogen peroxide dosing mouth, 717. pressure sensor, 718. air inlet 719.
Fig. 8 absorbing cabin top views：
The equally distributed bypass gas pipeline of 801. main pipeline 802~805.
(5) embodiment：
Specific embodiment：
Embodiment 1, a kind of device for producing nitric acid, it is characterised in that：
Its structure includes an active oxygen radical generator (201), an airflow line (204) and an absorbing cabin
(Fig. 7)；Wherein active oxygen radical generator has gas outlet (203)；Absorbing cabin has absorbing cabin air inlet (718), and absorbing cabin goes out
Gas port (719), dosing mouth (715), discharging opening (712), the gas outlet (203) of active oxygen radical generator is passed through airflow line
(204), airflow line (204) is passed through below absorbing cabin liquid levels from absorbing cabin air inlet (718).
Embodiment 2, a kind of device of production nitric acid as described in Example 1, it is characterised in that：
The active oxygen radical generator is that photodissociation catalysis storehouse (201) (can also use the other modes such as electrolysis
Produce active oxygen radical)；Wherein photodissociation catalysis storehouse includes uviol lamp (301), and ultraviolet light must not be irradiated in airflow line.
Embodiment 3, a kind of device of production nitric acid as described in Example 1, it is characterised in that：The ripple of uviol lamp (301)
A length of 220~350nm.
Embodiment 4, a kind of device of production nitric acid as described in Example 1, it is characterised in that：
The gas outlet (203) in photodissociation catalysis storehouse is located at airflow line close to absorbing cabin air inlet (718) place.Design gas outlet
The characteristics of be 1. to ensure that the ROS of generation was contacted and 2. protected with the nitrogen oxides in gas phase or gaseous state hydronitrogen in 0.1 second
Avoided after the NO_x formation for demonstrate,proving high-valence state by ultra violet lamp.
Embodiment 5, a kind of device of production nitric acid as described in Example 1, it is characterised in that：There is unsaturation in absorbing cabin
Salpeter solution and hydrogen peroxide solution.
Embodiment 6, a kind of device of production nitric acid as described in Example 1, it is characterised in that：
There are pressure valve (701) and pressure sensor (717) in absorbing cabin.
Embodiment 7, a kind of device of production nitric acid as described in Example 1, it is characterised in that：There is temperature biography in absorbing cabin
Sensor (710).
Embodiment 8, a kind of method for producing nitric acid, it is characterised in that：
The production of nitric acid can be divided into the three below stage：
First stage：Active oxygen radical is formed in active oxygen radical generator, and is input in airflow line；
Second stage：Gas phase oxidation process occurs for nitrogen oxides or gaseous state hydronitrogen in airflow line, and product leads to
Enter absorbing cabin；
Phase III：In absorbing cabin nitric acid is generated using liquid absorption gaseous nitrogen oxide.
Embodiment 9, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：
First stage：Active oxygen radical generator is a photodissociation catalysis storehouse, wherein using ozone formation active oxygen certainly
By base.
Embodiment 10, as described in Example 9 a kind of method for producing nitric acid, it is characterised in that：
The first stage：
(1) ozone is produced using compressed air, and Ozone transfer to photodissociation is catalyzed storehouse；
(2) ozone photodissociation is catalyzed into excited oxygen atom using uviol lamp in photodissociation catalysis storehouse；
(3) excited oxygen atom reacts to form active oxygen radical with vapor, triggers the chain reaction of free radical；Implement
Example 11, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：
The second stage：
(1) ozone gas comprising active oxygen radical of generation is passed through in airflow line, in described airflow line
Ultraviolet light should have been avoided；
(2) active oxygen radical is sufficiently mixed with nitrogen oxides or gaseous state hydronitrogen air-flow, in gas phase reaction, gas
State nitrogen oxides or gaseous state hydronitrogen react with active oxygen radical, so as to form the oxynitrides of more expensive state；
Embodiment 12, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：
The phase III：
(1) the oxynitrides mixed gas for the more expensive state for forming second stage is passed through absorbing cabin, utilizes unsaturation
Salpeter solution absorb；
(2) oxidant hydrogen peroxide is added in cabin is absorbed, with the ozone one of not participating in reaction of the part from photodissociation storehouse
Rise and provide oxidation environment for the solution in absorbing cabin；
(3) nitrogen oxides of high-valence state is converted generation nitric acid in absorbing liquid.
Embodiment 13, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：By the bag of generation
Ozone gas containing active oxygen radical was passed through in airflow line in 0.1 second.
Embodiment 14, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：The consumption of the ozone
Mol ratio with the nitrogen oxides of required oxidation is 0.3~1.0.
Embodiment 15, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：In the absorbing cabin
Hydrogen peroxide concentration need to be maintained at 150~250mmol/L.
A kind of method for producing nitric acid as described in Example 8 of embodiment 16., it is characterised in that：Nitre in the absorbing cabin
The concentration of acid is no more than 6mol/L.
A kind of method for producing nitric acid as described in Example 8 of embodiment 17., it is characterised in that：Described high-valence state nitrogen
Oxygen compound needs to contact with absorbing liquid in 0.1 second.
Embodiment 18, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：The height of described gas phase
Valence state nitrogen oxides residence time in absorbing cabin is more than or equal to 1 second.
Embodiment 19, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：Described absorbing liquid
Temperature range is to be less than or equal to 50 DEG C more than 0 DEG C.
Embodiment 20, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：The pressure of the absorbing cabin
Power is controlled in 2~6KPa.
Embodiment 21, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：The absorbing cabin nitric acid
The pH value of the aqueous solution is 2~4.
Embodiment 22, as described in Example 8 a kind of method for producing nitric acid, it is characterised in that：It is described to contain gaseous nitrogen
The gas of oxide is the industrial waste gas containing gaseous nitrogen oxide or gaseous state hydronitrogen.
Claims (22)
1. a kind of device for producing nitric acid, it is characterised in that：
Its structure includes an active oxygen radical generator, an airflow line and an absorbing cabin；Wherein active oxygen is free
Base generator has gas outlet；Absorbing cabin has absorbing cabin air inlet, absorbing cabin gas outlet, dosing mouth, discharging opening, active oxygen radical
The gas outlet of generator is passed through airflow line, and airflow line is passed through below absorbing cabin liquid levels from absorbing cabin air inlet.
2. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：
The active oxygen radical generator is a photodissociation catalysis storehouse；Wherein photodissociation catalysis storehouse includes uviol lamp, ultraviolet light
It must not be irradiated in airflow line.
3. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：The wavelength of uviol lamp be 220~
350nm。
4. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：
The gas outlet in photodissociation catalysis storehouse is located at airflow line close at absorbing cabin air inlet.
5. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：There is undersaturated nitric acid molten in absorbing cabin
Liquid and hydrogen peroxide solution.
6. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：
There are pressure valve and pressure sensor in absorbing cabin.
7. a kind of device of production nitric acid as claimed in claim 1, it is characterised in that：There is temperature sensor in absorbing cabin.
8. a kind of method for producing nitric acid, it is characterised in that：
The production of nitric acid can be divided into the three below stage：
First stage：Active oxygen radical is formed in active oxygen radical generator, and is input in airflow line；
Second stage：Gas containing gaseous nitrogen oxide or gaseous state hydronitrogen flows in airflow line, gaseous nitrogen oxygen
Gas phase oxidation process occurs for compound or gaseous state hydronitrogen, and product is passed through absorbing cabin；
Phase III：In absorbing cabin nitric acid is generated using liquid absorption high-valence state gaseous nitrogen oxide.
9. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：
First stage：Active oxygen radical generator is that a photodissociation is catalyzed in storehouse, wherein free using ozone formation active oxygen
Base.
10. a kind of method for producing nitric acid as claimed in claim 9, it is characterised in that：
The first stage：
(1) ozone is produced using compressed air, and Ozone transfer to photodissociation is catalyzed storehouse；
(2) ozone photodissociation is catalyzed into excited oxygen atom using uviol lamp in photodissociation catalysis storehouse；
(3) excited oxygen atom reacts to form active oxygen radical with vapor, triggers the chain reaction of free radical；
11. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：
The second stage：
(1) ozone gas comprising active oxygen radical of generation is passed through in airflow line, should be kept away in described airflow line
Exempt from have ultraviolet light；
(2) active oxygen radical is sufficiently mixed with nitrogen oxides or gaseous state hydronitrogen air-flow, in gas phase reaction, gaseous nitrogen
Oxide or gaseous state hydronitrogen react with active oxygen radical, so as to form the oxynitrides of more expensive state；
12. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：
The phase III：
(1) the oxynitrides mixed gas for the more expensive state for forming second stage is passed through absorbing cabin, utilizes undersaturated nitre
Acid solution absorbs；
(2) oxidant hydrogen peroxide is added in cabin is absorbed, is together with the ozone of not participating in reaction of the part from photodissociation storehouse
Solution in absorbing cabin provides oxidation environment；
(3) nitrogen oxides of high-valence state is converted generation nitric acid in absorbing liquid.
13. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：Active oxygen will be included described in generation
The ozone gas of free radical was passed through in airflow line in 0.1 second.
14. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The consumption and requisite oxygen of the ozone
The mol ratio of the nitrogen oxides of change is 0.3~1.0.
15. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：Hydrogen peroxide in the absorbing cabin is dense
Degree need to be maintained at 150~250mmol/L.
16. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The concentration of nitric acid in the absorbing cabin
No more than 6mol/L.
17. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：Described high-valence state oxynitrides
Need to contact with absorbing liquid in 0.1 second.
18. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The high-valence state nitrogen oxygen of described gas phase
Compound residence time in absorbing cabin is more than or equal to 1 second.
19. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The temperature range of described absorbing liquid
For more than 0 DEG C, less than or equal to 50 DEG C.
20. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The Stress control of the absorbing cabin is 2
~6KPa.
21. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：The absorbing cabin aqueous solution of nitric acid
PH value is 2~4.
22. a kind of method for producing nitric acid as claimed in claim 8, it is characterised in that：It is described containing gaseous nitrogen oxide or
The gas of gaseous state hydronitrogen is the industrial waste gas containing gaseous nitrogen oxide or gaseous state hydronitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710172151.9A CN107215854B (en) | 2017-03-22 | 2017-03-22 | Device and method for producing nitric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710172151.9A CN107215854B (en) | 2017-03-22 | 2017-03-22 | Device and method for producing nitric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107215854A true CN107215854A (en) | 2017-09-29 |
| CN107215854B CN107215854B (en) | 2022-02-11 |
Family
ID=59928234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710172151.9A Active CN107215854B (en) | 2017-03-22 | 2017-03-22 | Device and method for producing nitric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107215854B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333044A (en) * | 2020-03-10 | 2020-06-26 | 深圳市华星光电半导体显示技术有限公司 | Nitric acid production system and nitric acid production method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352644A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Wet flue gas denitration technique for nitrite recovery |
| CN102115253A (en) * | 2011-01-14 | 2011-07-06 | 中国环境科学研究院 | Novel multi-technology synergetic catalysis advanced micro-bubble ozone oxidation tower |
| CN102247750A (en) * | 2011-07-11 | 2011-11-23 | 华东理工大学 | Device and method for simultaneously desulfurizing and denitrifying flue gas by ozone catalytic oxidation process |
| CN104624028A (en) * | 2014-12-25 | 2015-05-20 | 江苏一环集团有限公司 | Coal combustion boiler flue gas denitrification device capable of recycling HNO3 solution |
| CN204824173U (en) * | 2015-05-26 | 2015-12-02 | 徐州工程学院 | Nitrogen oxide system nitric acid system in flue gas |
-
2017
- 2017-03-22 CN CN201710172151.9A patent/CN107215854B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352644A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Wet flue gas denitration technique for nitrite recovery |
| CN102115253A (en) * | 2011-01-14 | 2011-07-06 | 中国环境科学研究院 | Novel multi-technology synergetic catalysis advanced micro-bubble ozone oxidation tower |
| CN102247750A (en) * | 2011-07-11 | 2011-11-23 | 华东理工大学 | Device and method for simultaneously desulfurizing and denitrifying flue gas by ozone catalytic oxidation process |
| CN104624028A (en) * | 2014-12-25 | 2015-05-20 | 江苏一环集团有限公司 | Coal combustion boiler flue gas denitrification device capable of recycling HNO3 solution |
| CN204824173U (en) * | 2015-05-26 | 2015-12-02 | 徐州工程学院 | Nitrogen oxide system nitric acid system in flue gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333044A (en) * | 2020-03-10 | 2020-06-26 | 深圳市华星光电半导体显示技术有限公司 | Nitric acid production system and nitric acid production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107215854B (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Enhancement effects of O2− and OH radicals on NOX removal in the presence of SO2 by using an O3/H2O2 AOP system with inadequate O3 (O3/NO molar ratio= 0.5) | |
| CN102908883B (en) | A kind of flue gas and desulfurizing and denitrifying method | |
| Liu et al. | Removal of NO from flue gas using UV/S2 process in a novel photochemical impinging stream reactor | |
| Skalska et al. | Intensification of NOx absorption process by means of ozone injection into exhaust gas stream | |
| CN103537178B (en) | The treatment system of nitrotoleune nitric acid oxidation nitrogen oxide in tail gas and processing method | |
| Wang et al. | Oxidation absorption of hydrogen sulfide from gas stream using vacuum ultraviolet/H2O2/urea wet scrubbing system | |
| CN103977681A (en) | Denitration method for high-concentration nitric oxide flue gas | |
| CN104587809A (en) | Ozone-hydroxy free radical dry-wet combined desulphurization and denitration technology | |
| Guo et al. | Simultaneous removal of SO2 and NOx with ammonia combined with gas-phase oxidation of NO using ozone | |
| CN103736373A (en) | Flue gas treatment method and flue gas treatment device capable of simultaneous desulfurization, de-nitration and mercury removal through magnesium oxide | |
| KR102170628B1 (en) | System and Method for removing Nitrogen oxides and Sulfur dioxide in flue gas using gaseous chlorine dioxide | |
| CN105536467A (en) | Flue gas purification device and method combining photo-catalytic oxidization and double cyclic absorption | |
| CN205832945U (en) | A kind of nitrous oxides exhaust gas that reclaims prepares the device of dust technology | |
| CN110075690A (en) | A kind of novel oxynitrides tobacco remover and its application method | |
| WO2014008702A1 (en) | Method for treating nox-containing waste gas and system thereof | |
| CN101927126B (en) | Method for carrying out uncatalyzed direct oxidation treatment on gas containing nitric oxide by using Venturi oxidizer | |
| CN103230743B (en) | A kind of nitrogen oxide tail gas emission method | |
| Liu et al. | Advanced Oxidative Removal of Nitric Oxide from Flue Gas by Homogeneous Photo‐Fenton in a Photochemical Reactor | |
| CN105771652A (en) | Flue gas denitration method by taking manganese oxide as cyclic absorption medium | |
| CN105289236B (en) | A kind of technique based on hydrogen peroxide and the intensified-sintered flue gas synchronized desulfuring and denitrifyings of potassium permanganate oxidation NO | |
| CN104857852B (en) | VOCs removing method based on photocatalytic free radical advanced oxidation | |
| CN105498480A (en) | Ultraviolet radiation enhancement based method and device for simultaneous desulfurization, denitrification and particulate removal of pypocholoride | |
| CN105617857B (en) | A kind of PH3The low-temperature catalyzed reduction NO of selectivity method | |
| CN107215854A (en) | A kind of devices and methods therefor for producing nitric acid | |
| CN106669390B (en) | A kind of denitration process method of the process tail gas containing NOx |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |