CN112156646A - Time-phased gas inlet device for in-situ denitration in calcination process of copper-based oxygen carrier/catalyst precursor by taking nitrate as raw material - Google Patents
Time-phased gas inlet device for in-situ denitration in calcination process of copper-based oxygen carrier/catalyst precursor by taking nitrate as raw material Download PDFInfo
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- CN112156646A CN112156646A CN202010875011.XA CN202010875011A CN112156646A CN 112156646 A CN112156646 A CN 112156646A CN 202010875011 A CN202010875011 A CN 202010875011A CN 112156646 A CN112156646 A CN 112156646A
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- 238000001354 calcination Methods 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 239000007789 gas Substances 0.000 title claims abstract description 15
- 239000003546 flue gas Substances 0.000 claims abstract description 69
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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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
-
- 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
- B01D53/8696—Controlling the catalytic process
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01D2255/20761—Copper
-
- 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
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a time-phased gas inlet device for in-situ denitration in a copper-based oxygen carrier/catalyst precursor calcining process by taking nitrate as a raw material, belonging to the technical field of flue gas denitration. The time-sharing air inlet device for in-situ denitration in the calcination process of the copper-based oxygen carrier/catalyst precursor by taking nitrate as a raw material comprises a calcination hearth, a time-sharing air inlet part, a flue gas recirculation part, a control device and a flue gas purification device. According to the invention, the time-phased gas inlet and flue gas recirculation technology are coupled, so that the in-situ SCR denitration of the copper-based oxygen carrier is realized, and the generation of NOx is reduced.
Description
Technical Field
The invention relates to a time-phased gas inlet device for in-situ denitration in a copper-based oxygen carrier/catalyst precursor calcining process by taking nitrate as a raw material, belonging to the technical field of flue gas denitration.
Background
NOx is one of main pollutants discharged by the energy industry, the environmental problem is more and more emphasized in recent years, laws and regulations related to environmental protection are made and perfected in various countries, the emission standard of nitrogen oxides is increasingly strict, and the development of related technical research make internal disorder or usurp for reducing NOx emission has urgent needs and important significance. The flue gas recirculation can realize the control of the combustion temperature and the oxygen concentration, and improve the temperature field, the flow field and the like of the combustion chamber, thereby achieving the purposes of reducing emission and improving the combustion efficiency. The flue gas recirculation rate is generally controlled to be 10-20%, when a higher flue gas recirculation rate is adopted, the combustion is unstable, and the emission concentration of NOx can be reduced by 20-25%. Among the existing nitrogen oxide emission reduction technologies, the Selective Catalytic Reduction (SCR) technology has a high NOx removal rate (70% -90%), a low ammonia leakage rate (0-5 ppm) and a mature technology, and is widely applied in industry.
During the calcination process of the copper-based oxygen carrier preparation, nitrogen-containing components such as urea in the precursor can be combusted to generate a large amount of NOx and ammonia gas, so that the emission of pollutants is greatly increased. In the prior art, the efficiency of flue gas recirculation denitration is not high, the SCR technology needs a catalyst, the cost is high, equipment such as a reducing agent nozzle is needed, and the process is complex. Under the conditions of achieving high NOx removal rate and saving economic cost as much as possible, the problem of how to reduce the emission of nitrogen oxides in the process of calcining the copper-based oxygen carrier is important to solve.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a time-sharing air inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor by taking nitrate as a raw material. According to the invention, the time-phased gas inlet and flue gas recirculation technology are coupled, so that the in-situ SCR denitration of the copper-based oxygen carrier is realized, and the generation of NOx is reduced. The invention is realized by the following technical scheme.
A time-sharing air inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor by taking nitrate as a raw material comprises a calcination hearth 1, a time-sharing air inlet part, a flue gas recirculation part, a control device 14 and a flue gas purification device 16;
the time-interval air inlet part comprises an air pipeline temperature control switch 5 and CO2A pipeline temperature control switch 7, an air pipeline 8, a flue gas pipeline 9 and CO2A pipeline 10; the flue gas recirculation part comprises an electromagnetic valve I6 and a circulating fan 17;
a flue gas pipeline 9 inlet is arranged at a flue gas outlet of the calcining hearth 1, a control device 14 is arranged at the flue gas pipeline 9 inlet, the flue gas pipeline 9 is divided into two paths, one path is connected to a flue gas circulating inlet of the calcining hearth 1 through an electromagnetic valve I6 and a circulating fan 17, the other path is connected with a flue gas purifying device 16 through an electromagnetic valve II 15 and then is discharged, and a controller in the control device 14 controls the flow of the electromagnetic valve I6 and the flow of the electromagnetic valve II 15;
in the time-interval air inlet part, the upper side and the lower side of a flue gas circulation inlet end of a flue gas pipeline 9 are respectively communicated with CO2Line 10 and air line 8, CO2The pipeline 10 is connected with CO2Carrier gas, air line 8 connected to air, CO2The pipeline 10 is provided with CO2And an air pipeline temperature control switch 5 which is opened is arranged on the air pipeline 8 of the pipeline temperature control switch 7.
The air line 8 and CO2The pipe 10 is installed outside the flue gas pipe 9 through a fixing frame 11 and a connecting block 12.
And an air pipeline temperature control switch 5 which is opened at the outside at the temperature of 200-300 ℃ is arranged on the air pipeline 8.
The CO is2The pipeline 10 is provided with CO which is opened at 200-300 DEG C2And a pipeline temperature control switch 7.
The controller of the control device 14 is a conventional controller for controlling the flow rate of the solenoid valve. The control means 14 also includes conventional means for measuring the total smoke, which transmits data to the controller.
The working principle of the copper-based oxygen carrier/catalyst precursor in-situ denitration time-interval gas inlet device taking nitrate as a raw material in the calcining process is as follows:
(1) in the process of preparing the copper-based oxygen carrier/catalyst precursor in the calcining furnace 1 by taking nitrate as a raw material, a large amount of calcining flue gas generated by the calcining furnace 1 is discharged from a flue gas outlet of the calcining furnace 1, a controller of a control device 14 of the flue gas outlet of the calcining furnace 1 respectively controls the flow of an electromagnetic valve I6 and the flow of an electromagnetic valve II 15, 70-80% of the total amount of the calcining flue gas is purified by a flue gas purification device 16 and then discharged, and 20-30% of the total amount of the calcining flue gas is introduced into a flue gas circulation inlet of the calcining furnace 1 by a circulating fan 17;
(2) when the temperature of flue gas at the flue gas circulation inlet pipeline of the calcining furnace 1 is 200-300 ℃, CO2Pipeline temperature control switch 7 is turned on, CO2Passing carrier gas through CO2The pipeline 10 is conveyed to a flue gas circulation inlet of the calcining hearth 1 to calcine NOx and NH in flue gas3Taking a copper-based oxygen carrier/catalyst precursor generated in the calcining furnace 1 as a catalyst, and adding NOx and NH3Generating N2And H2O, achieving the aim of in-situ denitration;
(3) when the temperature of the flue gas at the flue gas circulation inlet pipeline of the calcining hearth 1 is 200-300 ℃, CO2The pipeline temperature control switch 7 is closed, the air pipeline temperature control switch 5 is opened, the air carrier gas is conveyed to the flue gas circulation inlet of the calcining hearth 1 through the air pipeline 10, and NOx and NH in the calcining flue gas3Taking a copper-based oxygen carrier/catalyst precursor generated in the calcining furnace 1 as a catalyst, and adding NOx and NH3Generating N2And H2And O, achieving the aim of in-situ denitration.
In the period of 200-300 ℃, a copper-based oxygen carrier/catalyst precursor is calcined to generate a large amount of NOx, and nitrogen-free carrier gas CO is automatically controlled through a temperature control switch2And the generation and emission of NOx can be greatly reduced by introducing the catalyst.
In a time period beyond 200-300 ℃, the copper-based oxygen carrier/catalyst precursor is calcined to generate less NOx, and relatively cheap carrier air is automatically controlled to be introduced through a temperature control switch, so that the discharge of NOx can be reduced, and the economic cost can be greatly saved.
The invention has the beneficial effects that: the automatic control of the time-sharing air inlet is realized through a temperature control switch, and C is introduced into a temperature range of 200-300 ℃ for generating a large amount of NOx in the process of calcining the copper-based oxygen carrier/catalyst precursorO2As the reaction atmosphere, the NOx generation amount is greatly reduced, and in other temperature intervals, relatively cheap air is introduced as the reaction atmosphere, so that the cost is saved while the NOx generation amount is low. By means of flue gas recirculation technology, NH contained in flue gas3The catalyst is used as a reducing agent to react with NOx, CuO is used as a catalyst, in-situ denitration in the calcining process of the copper-based oxygen carrier/catalyst precursor is realized, and the economic cost of the catalyst in the SCR technology and the process costs of storing and diluting the reducing agent, an ammonia injection system and the like are reduced. The method has the advantages of low investment, simple process and stable operation, meets the national emission standard of nitrogen oxides, realizes high-efficiency denitration and in-situ denitration of the copper-based oxygen carrier/catalyst precursor, reduces the comprehensive cost, and has obvious energy-saving and emission-reducing effects.
Drawings
FIG. 1 is a schematic diagram of a time-phased gas inlet device for in-situ denitration in a calcination process of a copper-based oxygen carrier/catalyst precursor using nitrate as a raw material according to the present invention;
FIG. 2 is a schematic view of the structure of the part of the invention which is air intake in different periods.
In the figure: 1-calcining furnace hearth, 2-tube wall, 3-sealing ring, 4-sealing mounting ring, 5-air pipeline temperature control switch, 6-electromagnetic valve I, 7-CO2Pipeline temperature control switch, 8-air pipeline, 9-flue gas pipeline, 10-CO2The device comprises a pipeline, 11 parts of a fixed frame, 12 parts of connecting blocks, 13 parts of time-sharing air inlet parts, 14 parts of a control device, 15 parts of electromagnetic valves II, 16 parts of a flue gas purification device and 17 parts of a circulating fan.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in fig. 1 to 2, the time-sharing gas inlet device for in-situ denitration in the calcination process of the copper-based oxygen carrier/catalyst precursor using nitrate as a raw material comprises a calcination furnace 1, a time-sharing gas inlet part, a flue gas recirculation part, a control device 14 and a flue gas purification device 16;
the time-interval air inlet part comprises an air pipeline temperature control switch 5 and CO2Temperature of pipelineControl switch 7, air pipeline 8, flue gas pipeline 9 and CO2A pipeline 10; the flue gas recirculation part comprises an electromagnetic valve I6 and a circulating fan 17;
a flue gas pipeline 9 inlet is arranged at a flue gas outlet of the calcining hearth 1, a control device 14 is arranged at the flue gas pipeline 9 inlet, the flue gas pipeline 9 is divided into two paths, one path is connected to a flue gas circulating inlet of the calcining hearth 1 through an electromagnetic valve I6 and a circulating fan 17, the other path is connected with a flue gas purifying device 16 through an electromagnetic valve II 15 and then is discharged, and a controller in the control device 14 controls the flow of the electromagnetic valve I6 and the flow of the electromagnetic valve II 15;
in the time-interval air inlet part, the upper side and the lower side of a flue gas circulation inlet end of a flue gas pipeline 9 are respectively communicated with CO2Line 10 and air line 8, CO2The pipeline 10 is connected with CO2Carrier gas, air line 8 connected to air, CO2The pipeline 10 is provided with CO2And an air pipeline temperature control switch 5 which is opened is arranged on the air pipeline 8 of the pipeline temperature control switch 7.
Wherein the air line 8 and CO2The pipeline 10 is arranged outside the flue gas pipeline 9 through a fixed frame 11 and a connecting block 12; an air pipeline temperature control switch 5 which is externally opened at 200-300 ℃ is arranged on the air pipeline 8; CO 22The pipeline 10 is provided with CO which is opened at 200-300 DEG C2And a pipeline temperature control switch 7.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (5)
1. A time-phased gas inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor by taking nitrate as a raw material is characterized in that: comprises a calcining hearth (1), a time-sharing air inlet part, a flue gas recirculation part, a control device (14) and a flue gas purification device (16);
the time-interval air inlet part comprises an air pipeline temperature control switch (5) and CO2Pipeline temperature control switch (7) and air pipeline(8) A flue gas pipeline (9) and CO2A pipeline (10); the smoke recirculation part comprises an electromagnetic valve I (6) and a circulating fan (17);
a flue gas pipeline (9) inlet is arranged at a flue gas outlet of the calcining hearth (1), a control device (14) is arranged at the flue gas pipeline (9) inlet, the flue gas pipeline (9) is divided into two paths, one path is connected to a flue gas circulating inlet of the calcining hearth (1) through an electromagnetic valve I (6) and a circulating fan (17), the other path is connected with a flue gas purifying device (16) through an electromagnetic valve II (15) and then is discharged, and a controller in the control device (14) controls the flow of the electromagnetic valve I (6) and the flow of the electromagnetic valve II (15);
in the time-interval air inlet part, the upper side and the lower side of a flue gas circulating inlet end of a flue gas pipeline (9) are respectively communicated with CO2Line (10) and air line (8), CO2The pipeline (10) is communicated with CO2Carrier gas, air pipe (8) connected with air, CO2CO is arranged on the pipeline (10)2A pipeline temperature control switch (7), and an air pipeline (8) is provided with an opened air pipeline temperature control switch (5).
2. The time-phased gas inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor using nitrate as a raw material according to claim 1, characterized in that: and a sealing ring (3) and a sealing mounting ring (4) are arranged at the joint of the pipe wall (2) of the calcining hearth (1) and the flue gas circulating inlet of the flue gas pipeline (9).
3. The time-phased gas inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor using nitrate as a raw material according to claim 1, characterized in that: the air line (8) and CO2The pipeline (10) is arranged outside the flue gas pipeline (9) through a fixing frame (11) and a connecting block (12).
4. The time-phased gas inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor using nitrate as a raw material according to claim 1, characterized in that: an air pipeline temperature control switch (5) which is opened at the outside at the temperature of 200-300 ℃ is arranged on the air pipeline (8).
5. The time-phased gas inlet device for in-situ denitration in the calcination process of a copper-based oxygen carrier/catalyst precursor using nitrate as a raw material according to claim 1, characterized in that: the CO is2The pipeline (10) is provided with CO which is opened at the temperature of 200-300 DEG C2A pipeline temperature control switch (7).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010875011.XA CN112156646B (en) | 2020-08-27 | 2020-08-27 | Copper-based oxygen carrier precursor calcines timesharing air inlet unit of normal position denitration |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010875011.XA CN112156646B (en) | 2020-08-27 | 2020-08-27 | Copper-based oxygen carrier precursor calcines timesharing air inlet unit of normal position denitration |
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| CN112156646B CN112156646B (en) | 2021-06-22 |
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2020
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| CN102000473A (en) * | 2010-11-26 | 2011-04-06 | 岳阳怡天化工有限公司 | Roast tail gas treatment method in production of catalytic cracking catalyst |
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| CN211159101U (en) * | 2019-09-30 | 2020-08-04 | 兖矿榆林精细化工有限公司 | Flue gas purification system after catalyst calcination |
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