CN114192158A - Preparation method of CO and NOx synergistic removal catalyst - Google Patents
Preparation method of CO and NOx synergistic removal catalyst Download PDFInfo
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- CN114192158A CN114192158A CN202111667715.9A CN202111667715A CN114192158A CN 114192158 A CN114192158 A CN 114192158A CN 202111667715 A CN202111667715 A CN 202111667715A CN 114192158 A CN114192158 A CN 114192158A
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
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- B01J35/56—
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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
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and 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
- B01D53/86—Catalytic processes
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/8646—Simultaneous elimination of the components
- B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01D2251/204—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a preparation method of a catalyst for removing CO and NOx synergistically. The invention relates to a catalyst capable of cooperatively catalyzing multiple pollutants and a preparation method thereof. By means of NH3And the reduction of CO, so that the catalyst can remove NOxMeanwhile, the method has a strong removing effect on CO in the flue gas, reduces a reaction temperature range, and belongs to the field of flue gas pollutant treatment.
Description
Technical Field
The invention belongs to the technical field of flue gas multi-pollutant removal catalysts, and particularly relates to a catalyst for removing CO and NOx in a synergistic manner, a preparation method of the catalyst and a method for removing harmful substances in flue gas by applying the catalyst.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In industrial processes, NOxAnd CO is a common pollutant in flue gas, posing a great threat to the environment and human health. It is not only toxic, but also may cause cancer and other diseases. Thus, NOxThe CO-treatment with CO is an important research direction
During the development of various denitration techniques in the past, NH3-SCR catalytic oxidation for NO removalxThe method has the advantages of low energy consumption and high selectivity, and is used for industrially removing NO at presentxOne of the most common methods. The SCR catalyst is the core of the technology, and the common catalysts comprise a noble metal catalyst, a nonmetal catalyst and a transition metal catalyst. At present, the vanadium-tungsten-titanium honeycomb catalyst has ultrahigh cost performance and is widely applied to industry. But NH3SCR has the disadvantages of ammonia slip and the like. And is easy to react with NH when the flue gas contains sulfur and water vapor3Reaction to form (NH)4)2SO3Therefore, the catalyst is inactivated due to accumulation on the surface of the vanadium-tungsten-titanium catalyst, and the service life of the catalyst is greatly shortened due to the blockage of an air preheater and the corrosion of equipment, so that the improvement of the sulfur resistance and the water resistance of the catalyst needs to be better solved. Due to NH3The disadvantage of SCR technology, CO-SCR using CO as a reductant has been a hotspot in recent years, CO-SCR being neither NH free3SCR is easy to cause the defects of catalyst poisoning, equipment blockage and the like, and does not contain NH3SCR has the disadvantage of being prone to carbon deposition and of low catalytic efficiency. In engineering practice, denitration is needed, a large amount of CO is contained in sintering machine or coke oven gas, and the denitration is needed, so that the NO is carried out simultaneously by using the catalyst with better sulfur resistance and water resistancexAnd the catalytic removal of CO, become a technology with wide application prospect.
Disclosure of Invention
Based on the technical background, the invention aims to provide a catalyst for the synergistic removal of CO and NOx, and the catalyst is prepared by a spraying method, so that the synergistic removal of harmful pollutants in flue gas can be realized, and good water-resistant and sulfur-resistant effects can be realized.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of a CO and NOx synergistic removal catalyst, wherein the catalyst is obtained by taking a vanadium-tungsten-titanium catalyst as a carrier, spraying a solution containing metal ions and acidity onto the surface of the carrier and roasting.
In the field, an impregnation method is usually adopted to load an active metal oxide on the surface of the SCR catalyst, however, the impregnation method requires a large amount of active metal salt solution to achieve the effect of full impregnation, and in addition, the mechanical property of the SCR catalyst may be damaged by adopting a soaking method. The research of the invention provides a mode of loading active metal in a spraying mode, which can effectively save the using amount of active metal salt solution.
The support of the first aspect may be a vanadium tungsten titanium catalyst, which is conventional in the art, and may be commercially available or prepared by itself. When the catalyst is used as a catalyst for removing flue gas, the carrier has a certain shape structure including but not limited to honeycomb shape, grid shape and the like, and the shape of the carrier is selected according to the use situation.
In a specific embodiment of the present invention, a method for preparing a vanadium-tungsten-titanium catalyst is provided, which comprises the following steps: uniformly mixing ammonium metavanadate, ammonium tungstate and metatitanic acid, adding water and glycerol to obtain a precursor mixture, mixing the precursors, kneading, and extruding into a honeycomb shape in a mold; and drying and roasting to obtain the vanadium-tungsten-titanium precursor.
Preferably, the specific steps of spraying the solution containing metal ions onto the surface of the carrier are as follows: and mixing the metal salt solution, adding an acid solution to adjust the pH value to 2-3 to obtain an active agent, and spraying the active agent onto the surface of the carrier through a rotary spraying device.
The invention proves that the loading effect of the metal ions can be improved by adopting the acidic active agent for spraying. Multiple experiments prove that when the pH value of the active agent solution is 2-3, the metal ions in the active agent are mixed more uniformly, the spraying effect on the carrier is the best, and the coating is firmest.
In an embodiment of the above preferred technical solution, the metal salt solution is a salt solution including copper ions, manganese ions, iron ions, and cerium ions, and the reason why the combination of the metal ions is selected is as follows: the mixed oxide of the metal ion combination has a very good effect on CO oxidation, and can also reduce the temperature interval of NO removal reaction.
Further, the acid radical carried in the metal salt is identical to the acid radical in the acid solution, and in a specific example, the nitrate ion, i.e. the metal salt solution, is a nitrate solution of copper ion, manganese ion, iron ion and cerium ion, and the acid solution is a dilute nitric acid solution.
In the metal salt solution, the ratio of the metal ions is Cu: mn: ce: fe is 0.8-1.2: 1.8-2.2: 0.08-0.12: 0.1-0.3%, the concentration of metal salt is 0.8-1.2%, and the concentration of the dilute nitric acid solution is 1-3%. In one example of the above embodiment, the specific steps of spraying the metal salt solution on the surface of the carrier are as follows:
(1) copper nitrate trihydrate, a 50% manganese nitrate solution, cerium nitrate hexahydrate, and iron nitrate nonahydrate were mixed in the following Cu: mn: ce: fe is 1: 2: 0.1: mixing at a ratio of 0.2, and adding water to obtain a metal salt solution with a concentration of 1%; adding a 2% dilute nitric acid solution into the metal salt solution to adjust the pH to 2-3, and uniformly stirring the solution after the pH adjustment at the temperature of 45-55 ℃ to obtain a light green metal salt solution, namely an active agent; adding the aqueous solution in the stirring process to keep the acidic environment of the metal salt solution unchanged;
(2) placing the vanadium-tungsten-titanium precursor on a base of a rotary spraying device, placing the active agent obtained in the step (1) into a container at the bottom of the rotary spraying device, and spraying through a spraying head, wherein the pressure of the spraying head is 4-6 bar, the rotating speed is 2-4 r/s, and the duration of the spraying process is 15-25 min.
The spraying parameters can ensure that the active agent enters the precursor honeycomb holes at a certain contact angle under the pressurization action of the rotary spraying device, so that a better loading effect is realized. In addition, the mixed liquid which is not successfully loaded is collected by a collecting device at the bottom of the rotary spraying device, and is pressurized by the pump again for spraying again, so that the active agent solution is effectively saved.
Preferably, the sprayed catalyst is dried and then roasted at 500-600 ℃ for 3-5 h to prepare the CO and NOx synergistic removal catalyst.
Further, the drying mode comprises natural airing and oven drying, in a specific example, the sprayed catalyst is placed in a cool and ventilated place for 10-14 hours to be naturally aired, and then is placed in an oven to be dried for 5-7 hours at the temperature of 100-120 ℃.
Further, the roasting temperature is 500-600 ℃, and the roasting time is 3-5 h.
In a second aspect of the present invention, there is provided a CO and NOx removal catalyst obtained by the preparation method of the first aspect.
Through the investigation of catalytic efficiency, the invention proves that the catalyst prepared by the method can effectively reduce the catalytic temperature of NOx, has better removal effect on CO while removing NOx, and when reducing gas NH is introduced3The concentration ratio of the carbon dioxide to CO is 1: and 5, the NOx removal effect is best. Compared with a pure vanadium-tungsten-titanium catalyst, the supported catalyst has greatly improved sulfur resistance and water resistance.
In a third aspect of the invention, the application of the CO and NOx removal catalyst of the second aspect in the field of flue gas treatment is provided.
The catalyst described above is preferably applied to a case where the two substances need to be treated simultaneously, such as flue gas treatment of sintering machine or coke oven gas, in the effect of removing CO and NOx synergistically by the catalyst described in the second aspect of the present invention.
The beneficial effects of one or more technical schemes are as follows:
1. the preparation of the precursor takes the existing industrial vanadium tungsten titanium catalyst as a template, the effect is not much different from the effect, and the modified honeycomb catalyst can be prepared by using the existing industrial vanadium tungsten titanium as the precursor for loading when being applied in large scale.
2. The invention can effectively control the emission of various pollutants in the flue gas, in particular NOxAnd CO. Reduction of NO by CO present in flue gas itselfxGreatly saves the cost of introducing reducing gas, reduces the damage of ammonia escape to the environment, and simultaneously compares with single NH3And in the case of SCR, the catalytic temperature interval is reduced, and the adaptability is wider.
3. Active agent Cu loaded in the invention1Mn2Fe0.1Ce0.2The catalytic oxidation effect on CO is close to that of a commercial hopcalite catalyst, but the cost is lower, the water-resistant and sulfur-resistant effect of the loaded catalyst is better, and the service life of the catalyst is greatly prolonged.
4. The invention uses the spraying method to carry out the loading preparation of the catalyst, and utilizes the physical characteristics to increase the momentum of the activator solution when contacting with the vertical surface of the precursor, thereby better improving the loading rate. The invention can save about 30% of the activator catalyst compared to vertical impregnation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the CO removal efficiency of the CO-removal catalyst in example 1 for a mixed gas;
FIG. 2 is a graph showing the removal efficiency of the synergistic removal catalyst for NO in a mixed gas as described in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, part of the flue gas treatment field is faced with simultaneous treatment of NOxAnd CO, the existing catalyst is often difficult to be superior to the removal of two harmful gases, and in order to solve the technical problems, the invention provides a CO and NOx synergistic removal catalyst.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) Taking ammonium metavanadate, ammonium tungstate and metatitanic acid, and uniformly mixing the ammonium metavanadate, the ammonium tungstate and the metatitanic acid according to a certain proportion.
(2) Deionized water and glycerol (release agent) are added to continuously knead the precursor mixture into a paste shape, and the paste shape is extruded on a die to form a honeycomb-shaped forming precursor. And then drying in the shade at a cool and dry place, then drying in an oven at 100 ℃ for 6 hours, then placing the hardened precursor in a muffle furnace, roasting at 300 ℃ for 2 hours, and roasting at 500 ℃ for 2 hours to obtain the final vanadium-tungsten-titanium precursor.
(3) 3.98g of copper nitrate trihydrate, 11.79g of 50% manganese nitrate solution, 0.72g of cerium nitrate hexahydrate and 1.33g of ferric nitrate nonahydrate were placed in a beaker, and 200ml of deionized water was added to make the concentration of metal nitrate in the mixed solution 1%. Then adding a small amount of HNO3Slightly stirring the solution to ensure that the pH value of the mixed solution reaches 2-3;
(4) and (3) placing the mixed liquid on a magnetic stirrer, stirring for 2 hours at 50 ℃ and 800r/min, adding deionized water every half hour, keeping the quality and the acid environment unchanged, uniformly stirring to form a light green nitrate mixed liquid, and then placing the mixed liquid in a dry place to be cooled to the normal temperature to be used as an active agent stock solution for later use.
(5) The precursor is fixed on a base of a rotary spraying device, and a rotary spraying nozzle is placed right above the catalyst. The active agent stock solution is put into a container at the bottom of a rotary spraying device, the stock solution is driven to a rotary spraying head by a vacuum pump, the stock solution is sprayed into divergent jet flow at the pressure of 5bar by the spraying head, and meanwhile, the spraying head keeps the rotating speed of 3r/s, so that the active stock solution generates a contact angle of 30 degrees when entering precursor honeycomb holes. The unsupported active agent mixed liquor is recovered by a bottom collecting device, and is pressurized by a pump for spraying again, and the process lasts for 20min until the sprayed catalyst is yellow green.
(6) And (3) naturally airing the sprayed catalyst in a shade and ventilated place for 12h, putting the aired catalyst into an oven to be dried for 6h at the temperature of 110 ℃, then putting the dried catalyst into a muffle furnace, and roasting for 4h at the temperature of 550 ℃ to obtain the modified honeycomb catalyst.
(7) Take 40cm3Placing the honeycomb catalyst into a reactor, and introducing 15000ml/min mixed gas (5% of O in the mixed gas)2、600ppmNH3、10000ppmCO、200ppmNO、20ppmSO2、N2Mixed with 10% steam) is introduced into the reactor, the concentration values of the gases of the bypass and the reaction path at different temperatures are measured, and the catalytic efficiency is calculated. In the embodiment, the mixed gas is introduced into the synergistic removal catalyst, and the pollutant removal efficiency of the reaction path after 5 hours is shown in fig. 1 and fig. 2.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the catalyst for removing CO and NOx synergistically is characterized in that the catalyst is obtained by taking a vanadium-tungsten-titanium catalyst as a carrier, spraying a solution containing metal ions onto the surface of the carrier and roasting.
2. The method for preparing the catalyst for the synergistic removal of CO and NOx according to claim 1, wherein the carrier is in a shape of honeycomb or grid, and the preparation method comprises the following steps: uniformly mixing ammonium metavanadate, ammonium tungstate and metatitanic acid, adding water and glycerol to obtain a precursor mixture, mixing the precursors, kneading, and extruding into a honeycomb shape in a mold; and drying and roasting to obtain the vanadium-tungsten-titanium precursor.
3. The method for preparing the catalyst for the synergistic removal of CO and NOx as claimed in claim 1, wherein the step of spraying the solution containing metal ions onto the surface of the carrier comprises the steps of: and mixing the metal salt solution, adding an acid solution to adjust the pH value to 2-3 to obtain an active agent, and spraying the active agent onto the surface of the carrier through a rotary spraying device.
4. The method for preparing a catalyst for the synergistic removal of CO and NOx as claimed in claim 1, wherein the metal salt solution is a salt solution comprising copper ions, manganese ions, iron ions and cerium ions;
preferably, the metal salt solution is a nitrate solution of copper ions, manganese ions, iron ions and cerium ions, and the acid solution is a dilute nitric acid solution.
5. The method for preparing a catalyst for the synergistic removal of CO and NOx as claimed in claim 4, wherein the ratio of the metal ions in the metal salt solution is Cu: mn: ce: fe is 0.8-1.2: 1.8-2.2: 0.08-0.12: 0.1-0.3%, the concentration of metal salt is 0.8-1.2%, and the concentration of the dilute nitric acid solution is 1-3%.
6. The method for preparing the catalyst for the synergistic removal of CO and NOx as claimed in claim 5, wherein the metal salt solution is sprayed on the surface of the carrier by the following steps:
(1) copper nitrate trihydrate, a 50% manganese nitrate solution, cerium nitrate hexahydrate, and iron nitrate nonahydrate were mixed in the following Cu: mn: ce: fe is 1: 2: 0.1: mixing at a ratio of 0.2, and adding water to obtain a metal salt solution with a concentration of 1%; adding a 2% dilute nitric acid solution into the metal salt solution to adjust the pH to 2-3, and uniformly stirring the solution after the pH adjustment at the temperature of 45-55 ℃ to obtain a light green metal salt solution, namely an active agent; adding the aqueous solution in the stirring process to keep the acidic environment of the metal salt solution unchanged;
(2) placing the vanadium-tungsten-titanium precursor on a base of a rotary spraying device, placing the active agent obtained in the step (1) into a container at the bottom of the rotary spraying device, and spraying through a spraying head, wherein the pressure of the spraying head is 4-6 bar, the rotating speed is 2-4 r/s, and the duration of the spraying process is 15-25 min.
7. The preparation method of the CO and NOx synergistic removal catalyst as claimed in claim 1, wherein the sprayed catalyst is dried and then calcined at 500-600 ℃ for 3-5 h to prepare the CO and NOx synergistic removal catalyst.
8. The preparation method of the catalyst for the synergistic removal of CO and NOx according to claim 7, wherein the drying manner comprises natural airing and oven drying, and in a specific example, the sprayed catalyst is naturally aired in a cool and ventilated place for 10-14 hours, and then is placed in an oven to be dried for 5-7 hours at the temperature of 100-120 ℃;
or, the roasting temperature is 500-600 ℃, and the roasting time is 3-5 h.
9. A CO and NOx removal catalyst obtained by the method of any one of claims 1 to 8.
10. The use of the CO and NOx removal catalyst in combination according to claim 9 in the field of flue gas treatment including but not limited to flue gas treatment of sintering machine or coke oven gas.
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