CN111318148A - Device and method for removing nitrate from dimethylamine or trimethylamine tail gas in heat-accumulating-type high-temperature oxidation furnace - Google Patents
Device and method for removing nitrate from dimethylamine or trimethylamine tail gas in heat-accumulating-type high-temperature oxidation furnace Download PDFInfo
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- CN111318148A CN111318148A CN202010327483.1A CN202010327483A CN111318148A CN 111318148 A CN111318148 A CN 111318148A CN 202010327483 A CN202010327483 A CN 202010327483A CN 111318148 A CN111318148 A CN 111318148A
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000003647 oxidation Effects 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000013589 supplement Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 75
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012855 volatile organic compound Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000001172 regenerating effect Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution 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
- B01D53/75—Multi-step processes
-
- 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
- B01D53/005—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 heat treatment
-
- 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
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- 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
-
- 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
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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
- B01D53/77—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
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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Abstract
The invention discloses a device and a method for removing nitrate from tail gas of a heat accumulating type high-temperature oxidation furnace by using dimethylamine or trimethylamine tail gas, and relates to the field of tail gas treatment of heat accumulating type high-temperature oxidation furnaces. The method comprises the following steps: the tail gas input device and the fresh air supplement device connected with the tail gas input device are connected with the heat accumulating type high-temperature oxidation furnace through a pipeline after fresh air is supplemented by the fresh air supplement device and mixed with the tail gas, and the heat accumulating type high-temperature oxidation furnace is connected with an alkali absorption device. The tail gas of dimethylamine or trimethylamine is used as a reducing agent and enters a heat accumulating type high-temperature oxidation furnace in a gaseous state, so that the effect of removing the nitrate from the tail gas of the heat accumulating type high-temperature oxidation furnace is realized.
Description
Technical Field
The invention relates to the field of tail gas treatment of heat accumulating type high-temperature oxidation furnaces, in particular to a device and a method for removing nitrate from dimethylamine or trimethylamine tail gas in a heat accumulating type high-temperature oxidation furnace.
Background
The main function of the RTO (regenerative thermal oxidizer) of the tail gas treatment facility is to remove VOCs (volatile organic compounds), nitrogen oxides are inevitably generated in the treatment process, and when the emission standard requirement of atmospheric pollutants is low, the nitrogen oxides can meet the emission standard, but when the emission standard requirement of the nitrogen oxides is increasingly improved, the denitration treatment is not carried out on the RTO (regenerative thermal oxidizer) tail gas, so that the emission standard of the nitrogen oxides is possibly exceeded.
In the prior art, a selective non-catalytic reduction denitration technology (SNCR for short) is used, and a reducing agent is used for reducing nitrogen oxides in flue gas into harmless nitrogen and water under the condition of no catalyst. The selective non-catalytic reduction means that under the action of no catalyst, a reducing agent is sprayed into a temperature window suitable for denitration reaction to reduce nitrogen oxides in the flue gas into harmless nitrogen and water. The technology generally adopts ammonia, urea or hydrogen ammonia acid sprayed in a furnace as a reducing agent to reduce NOx. The reductant reacts only with NOx in the flue gas and generally does not react with oxygen, and this technique does not employ a catalyst, so this method is referred to as selective non-catalytic reduction (SNCR). Since the process does not use a catalyst, the reducing agent must be added in the high temperature zone. And spraying the reducing agent into a region with the temperature of 850-1100 ℃ in the hearth, quickly thermally decomposing into NH3, and reacting with NOx in the flue gas to generate N2 and water.
In the prior art, a reducing agent containing amino needs to be supplemented, a spraying device needs to be installed, a 800-1100 ℃ temperature area in a hearth needs to be found accurately, the equipment investment is increased, and the operating chemical cost is increased.
Disclosure of Invention
The invention aims to provide a device and a method for removing nitrate from dimethylamine or trimethylamine tail gas in a heat accumulating type high-temperature oxidation furnace.
In order to realize the technical effects, the invention discloses a device for removing nitrate from dimethylamine or trimethylamine tail gas in a heat accumulating type high-temperature oxidation furnace, which comprises the following components: the tail gas input device and the fresh air supplement device connected with the tail gas input device are connected with the heat accumulating type high-temperature oxidation furnace through a pipeline after fresh air is supplemented by the fresh air supplement device and mixed with the tail gas, and the heat accumulating type high-temperature oxidation furnace is connected with an alkali absorption device.
Further, the tail gas input device is connected with the VOCs tail gas and the reduction tail gas.
The application also discloses a method for removing nitrate from the tail gas of the heat accumulating type high-temperature oxidation furnace by using the dimethylamine or trimethylamine tail gas, which is carried out by using the nitrate removing device.
And comprises the following steps:
(1) mixing tail gas, namely mixing tail gas containing dimethylamine and trimethylamine with organic tail gas;
(2) fresh air supplement, wherein fresh air is supplemented into the tail gas to be mixed;
(3) reacting in a heat accumulating type high-temperature oxidation furnace, introducing the mixed gas into the heat accumulating type high-temperature oxidation furnace, oxidizing volatile organic compounds through high-temperature oxidation, and reducing nitrogen oxides through reduction tail gas;
(4) and (4) alkali absorption, namely performing alkali absorption on the tail gas subjected to the high-temperature oxidation treatment through an alkali liquor pool, and then finishing the treatment for discharging.
Further, in the tail gas mixing step, dimethylamine or trimethylamine and organic tail gas are uniformly mixed in a gaseous form.
Further, the reaction is carried out in the zone of 750-1200 ℃ in the reaction process of the regenerative high-temperature oxidation furnace.
The invention has the beneficial effects that:
1. the invention is convenient to use, and omits the step of spraying the reducing agent;
2. the invention does not need the reducing agent to enter the system in a spraying mode, and the reducing agent is automatically and uniformly mixed;
3. the part where the nitrogen oxide is generated is just suitable for generating the reduction reaction, so long as the nitrogen oxide is generated, the nitrogen oxide can immediately generate the reduction reaction with the reducing agent, the denitration efficiency cannot be influenced due to the deviation of a temperature point, and the operation is more reliable;
4. the cost is lower than the investment of the additional spraying device or the selective catalytic reduction device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic view of a denitration apparatus according to the present invention.
Fig. 2 is a flow chart of the method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
as shown in fig. 1, a dimethylamine or trimethylamine tail gas used in denitration device of heat accumulating type high temperature oxidation furnace comprises: the tail gas input device 1 and the fresh air supplement device 2 connected with the tail gas input device are connected with the heat accumulating type high-temperature oxidation furnace 3 through a pipeline after fresh air and tail gas are supplemented by the fresh air supplement device and mixed, and the heat accumulating type high-temperature oxidation furnace is connected with the alkali absorption device 4.
Further, the tail gas input device is connected with the VOCs tail gas 101 and the reduction tail gas 102.
Example two:
a method for removing nitrate from tail gas of a heat accumulating type high-temperature oxidation furnace by using dimethylamine or trimethylamine tail gas is carried out by using the nitrate removing device.
And comprises the following steps:
(1) mixing tail gas, namely mixing tail gas containing dimethylamine and trimethylamine with organic tail gas;
(2) fresh air supplement, wherein fresh air is supplemented into the tail gas to be mixed;
(3) reacting in a heat accumulating type high-temperature oxidation furnace, introducing the mixed gas into the heat accumulating type high-temperature oxidation furnace, oxidizing volatile organic compounds through high-temperature oxidation, and reducing nitrogen oxides through reduction tail gas;
(4) and (4) alkali absorption, namely performing alkali absorption on the tail gas subjected to the high-temperature oxidation treatment through an alkali liquor pool, and then finishing the treatment for discharging.
Further, in the tail gas mixing step, dimethylamine or trimethylamine and organic tail gas are uniformly mixed in a gaseous form.
Further, the reaction is carried out in the zone of 750-1200 ℃ in the reaction process of the regenerative high-temperature oxidation furnace.
The method comprises the steps of taking tail gas generated in dimethylamine or trimethylamine production as a reducing agent containing amino, uniformly mixing the tail gas with other organic tail gas in a gas phase state, introducing the mixture into a hearth of an RTO (regenerative thermal oxidizer), and rapidly carrying out reduction reaction on the reducing agent and nitrogen oxide in flue gas to generate nitrogen and water under the high-temperature condition when the tail gas moves to a temperature range of 750-1200 ℃.
The method takes the whole hearth as a reactor, and the temperature change of the hearth is as follows: from the normal temperature at the inlet, the temperature of the outlet is reduced to be below 100 ℃ through a heat accumulator with the temperature of 750-1200 ℃, nitrogen oxide is generated in the first step in the processes of temperature rise, high-temperature maintenance and temperature reduction, the dimethylamine or trimethylamine is decomposed at high temperature, and the nitrogen oxide generated under the high-temperature condition synchronously performs reduction reaction with the dimethylamine or the trimethylamine to generate nitrogen and water. The denitration efficiency of the method can reach the efficiency of a selective catalytic reduction method (SCR method) (> 80%), and the method can fully meet the requirement of ultra-low emission standard of nitrogen oxides.
The reaction principle is as follows:
2NO + 2(CH3)2NH+ 14O2→ 2N2+ 7H2O+12CO2
2NO + 2NO2+ 4(CH3)2NH +15O2→ 4N2+ 12H2O+24CO2
6NO2+ 8(CH3)2NH +70O2→ 7N2+ 28H2O+48CO2
2NO + 2(CH3)3NH + 14O2→ 2N2+ 9H2O+6CO2
NO + NO2+ 2(CH3)3NH +9O2→ 2N2+ 9H2O+6CO2
6NO2+ 8(CH3)3NH + 6O2→ 7N2+ 24H2O+48CO2
tail gas generated in dimethylamine or trimethylamine production is used as a reducing agent and enters RTO (regenerative thermal oxidizer) in a gaseous state, so that the sufficient mixing and the uniform distribution are achieved. No extra spraying device is needed to spray the reducing agent to the RTO (regenerative thermal oxidizer). Because tail gas generated in dimethylamine or trimethylamine production enters an RTO (regenerative thermal oxidizer) and passes through all hearths, the tail gas can automatically participate in the reduction reaction at a position with proper temperature, and the position which is suitable for the reduction reaction in the hearths does not need to be tested and searched; the part where the nitrogen oxide is generated is just suitable for generating the reduction reaction, so long as the nitrogen oxide is generated, the nitrogen oxide can immediately generate the reduction reaction with the reducing agent, and the denitration efficiency is not influenced by the deviation of a temperature point.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (6)
1. A dimethylamine or trimethylamine tail gas is used for removing nitre device of heat accumulation formula high temperature oxidation furnace, its characterized in that includes: the tail gas input device (1) and a fresh air supplement device (2) connected with the tail gas input device are connected with the heat accumulating type high-temperature oxidation furnace (3) through a pipeline after fresh air is supplemented by the fresh air supplement device and mixed with the tail gas, and the heat accumulating type high-temperature oxidation furnace is connected with an alkali absorption device (4).
2. The device for removing nitrate from dimethylamine or trimethylamine tail gas in a heat accumulating type high temperature oxidation furnace according to claim 1, which is characterized in that: the tail gas input device is connected with VOCs tail gas (101) and reduction tail gas (102).
3. A method for removing nitrate from tail gas of a heat accumulating type high-temperature oxidation furnace by using dimethylamine or trimethylamine tail gas, which is characterized by using the nitrate removing device as claimed in claim 1 or 2.
4. The method for removing the nitrate from the tail gas of the heat accumulating type high-temperature oxidation furnace by using the dimethylamine or trimethylamine tail gas as the claimed in claim 3, wherein the method comprises the following steps: the method comprises the following steps:
(1) mixing tail gas, namely mixing tail gas containing dimethylamine and trimethylamine with organic tail gas;
(2) fresh air supplement, wherein fresh air is supplemented into the tail gas to be mixed;
(3) reacting in a heat accumulating type high-temperature oxidation furnace, introducing the mixed gas into the heat accumulating type high-temperature oxidation furnace, oxidizing volatile organic compounds through high-temperature oxidation, and reducing nitrogen oxides through reduction tail gas;
(4) and (4) alkali absorption, namely performing alkali absorption on the tail gas subjected to the high-temperature oxidation treatment through an alkali liquor pool, and then finishing the treatment for discharging.
5. The method for removing the nitrate from the tail gas of the heat accumulating type high-temperature oxidation furnace by using the dimethylamine or trimethylamine tail gas as the claimed in claim 3, wherein the method comprises the following steps: in the tail gas mixing step, dimethylamine or trimethylamine and organic tail gas are uniformly mixed in a gaseous form.
6. The method for removing the nitrate from the tail gas of the heat accumulating type high-temperature oxidation furnace by using the dimethylamine or trimethylamine tail gas as the claimed in claim 3, wherein the method comprises the following steps: in the reaction process of the heat accumulating type high-temperature oxidation furnace, the reaction is carried out in the furnace at the temperature of 750 ℃ and 1200 ℃.
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Cited By (1)
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CN113578023A (en) * | 2021-08-03 | 2021-11-02 | 福建省福能龙安热电有限公司 | Method and device for treating nitrogen oxides in boiler waste gas by using dimethylamine waste liquid |
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CN212091629U (en) * | 2020-04-23 | 2020-12-08 | 山东科源化工有限公司 | Dimethylamine or trimethylamine tail gas is used for heat accumulation formula high temperature oxidation furnace denitration device |
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- 2020-04-23 CN CN202010327483.1A patent/CN111318148A/en active Pending
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