US20110150742A1 - Catalysts for nox reduction employing h2 and a method of reducing nox - Google Patents

Catalysts for nox reduction employing h2 and a method of reducing nox Download PDF

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Publication number
US20110150742A1
US20110150742A1 US13/056,281 US200813056281A US2011150742A1 US 20110150742 A1 US20110150742 A1 US 20110150742A1 US 200813056281 A US200813056281 A US 200813056281A US 2011150742 A1 US2011150742 A1 US 2011150742A1
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Prior art keywords
catalyst
mixed oxide
metal
amount
reduction
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US13/056,281
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Inventor
Hyun-Sik Han
Eun-seok Kim
Gon Seo
Se-Min Park
Yun-Je Lee
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Heesung Catalysts Corp
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Heesung Catalysts Corp
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Assigned to HEESUNG CATALYSTS CORPORATION reassignment HEESUNG CATALYSTS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAN, HYUN-SIK, KIM, EUN-SEOK, LEE, YUN-JE, PARK, SE-MIN, SEO, GON
Publication of US20110150742A1 publication Critical patent/US20110150742A1/en
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    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/9427—Processes characterised by a specific catalyst for removing nitrous oxide
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Definitions

  • SCR selective catalytic reduction
  • NSR NO x storage reduction
  • NO x emitted from large-scale boilers or nitric acid plants can be effectively removed through NH 3 -SCR which supplies ammonia as a reducing agent to a catalyst bed composed of titania-supported vanadia or iron-containing zeolite.
  • Ammonia is highly reactive and selective and is thus very effective for removing NO x from the exhaust gas of fixed facilities even in the presence of O 2 .
  • the use of ammonia to remove NO x from diesel exhaust gas is very dangerous because a diesel vehicle should be driven in a state of always being loaded with ammonia which is highly toxic. So, aqueous urea is used instead of ammonia as a reducing agent therein.
  • the urea is decomposed into ammonia and carbon dioxide in the catalyst bed so that NO x is reduced to N 2 .
  • the urea-SCR method is advantageous because NO x removal performance is high, it is problematic in that a tank for storing aqueous urea and a device for spraying such urea should be additionally mounted to a diesel vehicle. As has been done for fuel, a sales network of aqueous urea should be constructed. As well, the urea-SCR method is difficult to apply to a diesel vehicle, due to problems including low solubility of urea, freezing, and ammonia slip.
  • H 2 -SCR using H 2 as a reducing agent instead of the aqueous urea is receiving attention because the construction of an apparatus thereof is simple and there is no concern about secondary pollution.
  • O 2 in the diesel exhaust gas may first react with H 2 , undesirably lowering NO x selective removal efficiency by H 2 .
  • the application of the above method has not been considered to date. The reason is described below.
  • the temperature and O 2 content of diesel exhaust gas greatly vary depending on driving conditions of vehicles.
  • the temperature may be 300° C. or higher and also the O 2 content may exceed 10% under lean burn.
  • H 2 should be strongly activated. In this case, however, a probability of reacting such H 2 with O 2 is increased, undesirably lowering the NO x removal efficiency. Namely, to increase the NO x removal efficiency by H 2 , the probability of reacting H 2 with O 2 should be inhibited while increasing the degree of activation of H 2 , which is difficult.
  • limitations are imposed on applying the H 2 -SCR method to diesel vehicles.
  • the present inventors have directed their attention to a method of reducing NO x using H 2 as a reducing agent in the presence of ammonia, in lieu of conventional direct NO x reduction by H 2 , to selectively reduce NO x while inhibiting excessive activation of H 2 .
  • the present inventors have devised two-step NO 2 removal, including activating H 2 only to the appropriate level so that it can thus react with NO x , giving ammonia, which is then reacted with NO x .
  • an object of the present invention is to provide a catalyst composition for reducing NO x through two steps including reacting NO x with H 2 , thus preparing ammonia, which is then reacted with NO x , thereby removing NO x , instead of direct NO x reduction by H 2 .
  • Another object of the present invention is to provide a hybrid catalyst composition having not only a function as an SCR catalyst of reaction between a reducing agent and NO x but also an NSR function for storing NO x on the surface of the catalyst to thus react with the reducing agent, so that part of the reducing agent is adsorbed on the surface of the catalyst and thus NO x storage sites are formed, in order to efficiently remove NO x regardless of changes in the concentration of NO x .
  • a further object of the present invention is to provide a catalyst composition suitable for a H 2 -SCR method using H 2 as a reducing agent including the two steps of producing ammonia and then removing NO x , in which the temperature range of the catalyst composition usable in diesel vehicles is wide and is on the order of 150 ⁇ 300° C.
  • Still another object of the present invention is to provide a catalyst composition including the catalyst composition according to the present invention and a conventional NH 3 -SCR catalyst composition, which are mixed together.
  • Yet another object of the present invention is to provide a method of reducing NO x using the catalyst composition.
  • the present invention provides a mixed oxide catalyst, a method of preparing the catalyst and a method of reducing NO x using the catalyst.
  • the mixed oxide catalyst for reducing NO x using H 2 as a reducing agent includes one or more selected from the group of A metal oxides consisting of Fe 2 O 3 , CO 2 O 3 , NiO and CuO, and one or more selected from the group of B metal oxides consisting of V 2 O 5 , Cr 2 O 3 , MnO 2 and MoO 3 , which are co-precipitated and mixed.
  • the present invention has the following features, but is not limited thereto.
  • the weight ratio of A metal oxide to B metal oxide may range from 2:1 to 1:0.5.
  • a precious metal selected from the group consisting of Pt and Pd may be supported in an amount of 0.1 ⁇ 2 wt %.
  • the mixed oxide catalyst may further include a conventional NH 3 -SCR catalyst.
  • a conventional NH 3 -SCR catalyst may include, but is not limited to, a titania-supported vanadia catalyst or an iron-containing zeolite catalyst.
  • the method of preparing the mixed oxide catalyst for reducing NO x using H 2 as a reducing agent includes dissolving in aqueous nitrate or acetate one or more metal oxide precursors selected from the group of A metal oxides consisting of Fe 2 O 3 , Co 2 O 3 , NiO and CuO, and one or more metal oxide precursors selected from the group of B metal oxides consisting of V 2 O 5 , Cr 2 O 3 , MnO 2 and MoO 3 , thus obtaining a solution, adding barium nitrate for improving structural stability of the mixed oxide to the solution, adding ammonia water or aqueous sodium bicarbonate as a precipitating agent to the solution so that pH of the solution is 7 ⁇ 7.3, thus forming a precipitate, and subjecting the precipitate to post treatment including filtering, washing, drying and burning.
  • the present invention has the following features, but is not limited thereto.
  • the ratio of A metal oxide precursor to B metal oxide precursor may range from 2:1 to 1:0.5.
  • the method may further include, after subjecting the precipitate to post treatment, supporting either or both precious metals of Pt and Pd in an amount of 0.1 ⁇ 2 wt % on the catalyst, burning the precious metal-supported catalyst, and subjecting the burned catalyst to reduction treatment using a gas mixture containing N 2 and H 2 at a molar ratio of 1.
  • the method of reducing NO x includes reducing NO x at 150 ⁇ 350° C. using H 2 as a reducing agent in the presence of the above mixed oxide catalyst. This method may be performed even under conditions in which O 2 content is 0 ⁇ 10% by volume based on the volume of NO x , but the present invention is not limited thereto.
  • oxides of A metals including Cu, Fe, Co and Ni and oxides of B metals including Cr, Mn, Mo and V are co-precipitated and mixed, thus preparing mixed oxide catalysts and ternary mixed oxide catalysts.
  • These catalysts exhibit superior activity for production of ammonia through selective reaction between NO 2 and H 2 even in the presence of 5% or 10% O 2 , and simultaneously, manifest very high NO 2 and NO storage performance.
  • the catalysts can exhibit superior NO x reduction performance through injection of H 2 even in the presence of O 2 .
  • the NO x removal performance is high.
  • the catalysts according to the present invention have high Pt or Pd dispersability and high hydrothermal stability and poisoning resistance to sulfur and thus can significantly remove NO x from diesel exhaust gas. Also, the catalysts can be typically easily prepared from transition metal precursors which are inexpensive with high durability to water or heat and to sulfur poisoning.
  • FIG. 1 shows X-ray diffraction patterns of A-B mixed oxide catalysts in which the B metal is Cr and the A metal is Fe, Co, Ni and Cu, after a burning process;
  • FIG. 2 shows X-ray diffraction patterns of A-B mixed oxide catalysts in which the A metal is Cu and the B metal is Cr, V, Mo and Mn, a Cr—Mn catalyst, and a Fe—Mn catalyst, after a burning process;
  • FIG. 3 shows X-ray diffraction patterns of Pt(2.0)-Cu—Cr and Pt(2.0)-Fe—Mn catalysts, which are Pt-supported catalysts;
  • FIG. 4 shows IR spectra of the process of storing NO 2 (a) and the process of reducing NO 2 by H 2 (b) in the Cu—Cr catalyst;
  • FIG. 5 shows IR spectra of the process of producing ammonia from NO 2 through injection of H 2 in the absence of O 2 (a) and in the presence of O 2 (b) in the Cu—Cr catalyst which is a mixed oxide catalyst;
  • FIG. 6 shows IR spectra of the Cu—Mn catalyst, the Fe—Cr catalyst and the Fe—Mn catalyst in the presence of O 2 ;
  • FIG. 7 schematically shows a flow reactor used for H 2 -SCR
  • FIG. 8 shows NO 2 reduction results by H 2 of the Pt(2.0)-Fe catalyst (a), the Pt(2.0)-Mn catalyst (b) and the Pt(2.0)-Fe—Mn catalyst (c) under flow of 500 ppm NO 2 containing 10% O 2 ;
  • FIG. 9 shows NO 2 reduction behavior by H 2 of the Pt(2.0)-Fe—Mn catalyst with Fe-BEA zeolite.
  • a catalyst for effectively and selectively reducing NO x using H 2 gas in the presence of O 2 should have the following three functions, namely, high NO x adsorption, appropriate activation of H 2 , and activation of adsorbed NO x .
  • NO x is adsorbed or stored on the surface of the catalyst because of having reacted therewith and thus should be concentrated on the catalyst.
  • part of NO x should be activated so that it is converted into ammonia through reaction with H 2 .
  • H 2 when H 2 is adsorbed on the surface of the catalyst and thus activated in an atomic state, it may be reacted with NO x , thus producing ammonia.
  • the present inventors selected, as oxides of A metals which exhibit superior NO x storage performance, Fe 2 O 3 , CO 2 O 3 , NiO and CuO, and as oxides of B metals which are able to adsorb NO x in an activated state, V 2 O 5 , Cr 2 O 3 , MnO 2 and MoO 3 .
  • the oxides of the A and B metals are co-precipitated and combined, thus preparing mixed oxides, thereby maximizing NO x storage capacity and NO x reduction performance at the same time.
  • barium nitrate is added as a structure stabilizer.
  • the catalyst As a precious metal, Pt or Pd is supported on the catalyst. Depending on the type of catalyst, two or more kinds of A metal or B metal are added, thus preparing ternary or more mixed oxide catalysts, after which a precious metal is supported thereon. Accordingly, H 2 is activated in an atomic state on the surface of precious metal to thus react with NO x adsorbed on the surface of the mixed oxide, thereby producing ammonia.
  • the mixed oxide according to the present invention promotes the ammonia and NO x reduction and ultimately reduces NO x to N 2 .
  • the mixed oxide catalyst For mass production of the mixed oxide catalyst at low cost, a general co-precipitation method is applied, and inexpensive starting materials are used.
  • ammonia water or sodium bicarbonate is added to the mixed solution to appropriately adjust the pH of the solution, a highly active catalyst is prepared.
  • the precious metal is supported in an amount of 0.1 ⁇ 2%, and the reduction reaction is operated in the temperature range of 150 ⁇ 350° C. Even when the concentration of O 2 in NO x exceeds 10% by volume, the above catalyst can exhibit superior NO x selective reduction by H 2 .
  • Mixed oxide catalysts were prepared from oxides of A metals (Cu, Fe, Co, Ni) and B metals (Cr, Mn, Mo, V) through co-precipitation and mixing.
  • the weight ratio of A metal oxide to B metal oxide was adjusted to 2, 1 and 0.5.
  • As a precipitating agent ammonia water or aqueous sodium bicarbonate was used, and pH of the mixed solution was adjusted to 6.0 ⁇ 8.0. Any one A metal was reacted with any one B metal, thus preparing binary mixed oxide catalysts, and also, multicomponent mixed oxide catalysts were prepared using two or more kinds of these metals. The method of preparing some catalysts which are regarded as important is described below.
  • a solution of 15.2 g of copper nitrate and 1.60 g of barium nitrate in 152 g of water was mixed with a solution of 15.4 g of potassium dichromate in 154 g of water, thus preparing a mixed solution.
  • the mixed solution was stirred for 30 min and then ammonia water was slowly added thereto so that the pH thereof was 7.0 ⁇ 7.5.
  • the resultant precipitate was filtered using filter paper, sufficiently dried in an oven at 80° C., and then ground using a mortar and a pestle, thus obtaining fine powder.
  • the powder was transferred into an electric furnace so that it was burned at 500° C. for 4 hours, giving 10.9 g of a Cu—Cr mixed oxide catalyst represented by a Cu—Cr catalyst.
  • a solution of 24.7 g of iron nitrate and 1.6 g of barium nitrate in 247 g of water and a solution of 15.4 g of potassium dichromate in 154 g of water were prepared. These two solutions were mixed and stirred for 30 min to provide for sufficient mixing, after which ammonia water was slowly added thereto so that the pH thereof was 7.0 ⁇ 8.0.
  • the resultant precipitate was filtered using filter paper, dried in an oven at 80° C., and then ground using a mortar and a pestle, thus obtaining fine powder.
  • the powder was transferred into an electric furnace so that it was burned at 500° C. for 4 hours, giving 8.5 g of a Fe—Cr mixed oxide catalyst represented by a Fe—Cr catalyst.
  • a solution of 20.6 g of copper nitrate in 206 g of water and a solution of 24.6 g of manganese nitrate in 246 g of water were prepared. These two solutions were sufficiently mixed for 30 min, after which a 1 M sodium bicarbonate solution was slowly added thereto so that the pH thereof was 7.0 ⁇ 7.8.
  • the resultant precipitate was filtered using filter paper, dried in an oven at 80° C., and then ground using a mortar and a pestle, thus obtaining fine powder.
  • the powder was transferred into an electric furnace so that it was burned at 500° C. for 4 hours, giving 21 g of a Cu—Mn mixed oxide catalyst represented by a Cu—Mn catalyst.
  • a solution of 35.9 g of iron nitrate in 359 g of water and a solution of 25.5 g of manganese nitrate in 255 g of water were prepared. These two solutions were sufficiently mixed for 30 min, after which a 1 M sodium bicarbonate solution was slowly added thereto so that the pH thereof was 6.5 ⁇ 7.5.
  • the resultant precipitate was filtered using filter paper, dried in an oven at 80° C., and then ground using a mortar and a pestle, thus obtaining fine powder.
  • the powder was transferred into an electric furnace so that it was burned at 500° C. for 4 hours, giving 15 g of a Fe—Mn mixed oxide catalyst represented by a Fe—Mn catalyst.
  • a solution of 17.6 g of manganese nitrate and 1.6 g of barium nitrate in 176 g of water and a solution of 15.4 g of potassium dichromate in 154 g of water were prepared. These two solutions were mixed and stirred for 30 min to provide for sufficient mixing, after which ammonia water was slowly added thereto so that the pH thereof was 7.0 ⁇ 7.5.
  • the resultant precipitate was filtered using filter paper, dried in an oven at 80° C., and then ground using a mortar and a pestle, thus obtaining fine powder.
  • the powder was transferred into an electric furnace so that it was burned at 500° C. for 4 hours, giving 12.1 g of a Mn—Cr mixed oxide catalyst represented by a Mn—Cr catalyst.
  • the other mixed oxide catalysts were prepared through the above procedures. Also, mixed oxide catalysts having a composition ratio of 2 and 0.5, in addition to 1, were prepared. Each of the catalysts thus prepared was reduced under flow of a reducing gas mixture containing H 2 and N 2 at a molar ratio of 1:1 at 400° C. and a flow rate of 120 ml/min, before being used.
  • Pt was supported in an amount of 0.1, 0.2, 1.0 and 2.0% by weight on the mixed oxide catalyst of Example 1.
  • a Pt precursor hexachloroplatinic acid was dissolved in an amount of each of 0.1, 0.2, 1.1 and 2.1 g in 35 g of water, thus preparing a Pt solution, which was then added to 50 g of the mixed oxide catalyst.
  • the catalyst reached equilibrium after 24 hours, and then dried in an oven at 80° C. and thus dewatered.
  • the solution was burned in an electric furnace at 400° C. for 2 hours, placed in a quartz tube and then subjected to reduction treatment using a gas mixture containing N 2 and H 2 mixed at an equal ratio.
  • the Pt-supported Cu—Cr catalysts and Fe—Mn catalysts were represented by Pt(0.1)-Cu—Cr, Pt(0.2)-Cu—Cr, Pt(1.0)-Cu—Cr, Pt(2.0)-Cu—Cr, Pt(0.1)-Fe—Mn, Pt(0.2)-Fe—Mn, Pt(1.0)-Fe—Mn, and Pt(2.0)-Fe—Mn.
  • Pd-supported mixed oxide catalysts were prepared using a palladium nitrate precursor through procedures similar to the above Pt supporting procedures. Specifically, palladium nitrate was dissolved in an amount of each of 0.1, 0.2, 1.1 and 2.2 g in 35 g of water, thus preparing a Pd solution which was then added to 50 g of the mixed oxide catalyst, dried, burned in an electric furnace at 400° C. for 2 hours, and then subjected to reduction treatment, yielding Pd-supported mixed oxide catalysts.
  • the Pd-supported Cu—Cr catalysts and Fe—Mn catalysts were represented by Pd(0.1)-Cu—Cr, Pd(0.2)-Cu—Cr, Pd(1.0)-Cu—Cr, Pd(2.0)-Cu—Cr, Pd(0.1)-Fe—Mn, Pd(0.2)-Fe—Mn, Pd(1.0)-Fe—Mn, and Pd(2.0)-Fe—Mn.
  • Example 1 the catalysts in which the B metal was Cr and the A metal was Fe, Co, Ni and Cu were burned, after which X-ray diffraction patterns thereof were measured.
  • the results are shown in FIG. 1 .
  • the diffraction pattern of the mixed oxide catalyst was very complicated because the diffraction peaks of metal oxides alone and in combinations thereof coexisted.
  • the diffraction peaks of CuO, CuCr 2 O 4 and BaCrO 4 were shown.
  • the diffraction peak of BaCrO 4 added to improve structural stability of the catalyst was distinctly observed.
  • FIG. 2 shows the X-ray diffraction patterns of the A-B mixed oxide catalysts in which the A metal was set and the kind of B metal was changed to Cr, V, Mo and Mn.
  • the diffraction peaks of Cu 2 V 2 O 7 and V 2 O 5 were observed.
  • the peak of CuO and CuMnO 4 was observed together.
  • the diffraction peak of the copper compound was unclear, and only the diffraction peaks of MoO 2 and MoO 3 were greatly observed.
  • the diffraction peaks of the Cr—Mn catalyst prepared from only B metals and the Fe—Mn catalyst prepared through crossing of A-B metals were observed.
  • the diffraction pattern of the catalyst was seen to considerably vary.
  • the diffraction peaks of CuO and CuMnO 4 were observed, whereas in the Cr—Mn catalyst the diffraction peaks of MnO 2 and BaCrO 4 were observed.
  • the diffraction peaks of Fe 2 O 3 and NaMnO 4 were observed. From this, the oxides of A and B metals could be seen to be present in different forms depending on the kind of metal.
  • FIG. 3 shows X-ray diffraction patterns of, as Pt-supported catalysts, Pt(2.0)-Fe, Pt(2.0)-Mn, Pt(2.0)-Fe—Mn, Pt(2.0)-Fe—Mn(2/1) and Pt(2.0)-Fe—Mn(1/2) having different Fe/Mn composition ratios, and Pt(2.0)-Cu—Cr catalysts, and as a Pd-supported catalyst, Pd(2.0)-Fe—Mn, which were prepared in Example 2.
  • Pt(2.0)-Fe catalyst the diffraction peaks of NaFeO 2 and Fe metal were observed.
  • the Pt(2.0)-Mn catalyst the diffraction peaks of MnO were greatly observed.
  • the Pt(2.0)-Cu—Cr catalyst had complicated diffraction peaks, unlike the Cu—Cr catalyst.
  • the diffraction peak of Pt in all of these catalysts was not observed. This was judged to be because Pt did not aggregate on the surface of the catalyst but was well dispersed thereon.
  • the NO 2 storage performance of the catalysts prepared in Examples 1 and 2 was evaluated. To this end, the catalyst was loaded into a gravimetric adsorption system provided with a quartz spring and then exhausted at 300° C. for 1 hour, after which measurement was performed at 150° C. in consideration of the temperature of diesel exhaust gas.
  • the results of measurement of the storage performance of the Cu—Cr catalyst and the Fe—Mn catalyst among the above mixed oxide catalysts are summarized in Table 1 below.
  • the NO 2 storage performance of the catalyst was greatly changed depending on catalyst pretreatment conditions. The storage performance was represented into a storage amount in a state where the catalyst was exposed to NO 2 at 30 Torr and a storage amount in a state where NO 2 was emitted. Before reduction treatment, an adsorption amount was slightly larger than the storage amount.
  • the adsorption amount became similar to the storage amount. This is considered to be because part of NO 2 is weakly adsorbed on the surface of the catalyst before the reduction treatment, but the entirety thereof is strongly stored thereon after the reduction treatment.
  • the performance of the catalyst was determined only by the storage amount with no consideration being given to the adsorption amount.
  • the amount of stored NO 2 was increased about 23 times from 7 mg/g to 161 mg/g through reduction treatment.
  • the amount of stored NO 2 was increased about 6 times from 13 mg/g to 79 mg/g through the reduction treatment.
  • the Fe—Mn mixed oxide catalyst containing these two components increased the storage amount about 7 times before the reduction treatment but about 2 times after the reduction treatment, compared to that of the catalyst composed exclusively of Fe or Mn.
  • the amount of stored NO 2 was remarkably larger than that of the Cu—Cr catalyst, and thus the NO 2 storage performance could be seen to greatly vary depending on the kind of metal.
  • NO 2 may be typically adsorbed in a large amount on many O vacancies formed on the surface of the catalyst after the reduction treatment.
  • the amount of NO 2 stored on the Fe—Mn catalyst was 174 mg/g, which was evaluated to be superior.
  • Table 1 shows the NO 2 adsorption and storage amounts of the mixed oxide catalysts at 50° C.
  • the amount of stored NO 2 was greatly changed.
  • the amount of stored NO 2 was 254 mg/g, which was esteemed to be very high.
  • the Pt(2.0)-Mn catalyst also increased the storage amount from 79 mg/g to 106 mg/g, which was smaller than that of the Pt(2.0)-Fe catalyst.
  • the Pt(2.0)-Fe—Mn catalyst slightly increased the storage amount from 170 mg/g to 181 mg/g, compared to that of the Fe—Mn catalyst containing no Pt.
  • the Cu—Cr catalyst slightly decreased the storage amount from 43 mg/g to 36 mg/g when Pt was supported thereon. This is considered to be because, when Pt is supported, the activation of H 2 is increased upon reduction treatment and thus many O vacancies of the surface of the catalyst are formed.
  • the amount of stored NO 2 was decreased, and thus the storage performance of the catalyst could be seen to greatly vary depending on the kind of metal.
  • the storage state of the adsorbed NO was checked using an IR spectrometer (BIO-RAD, 175C) equipped with an in-situ cell.
  • the NO 2 storage behavior and the NO 2 desorption behavior by H 2 in the Pt(2.0)-Cu—Cr catalyst of Example 1 are shown in FIG. 4 .
  • the reduction treatment was performed at 250° C. using H 2 at a flow rate of 100 ml/min, after which 2000 ppm NO 2 by volume was allowed to flow at 200° C. and thus the process of storing NO 2 was measured (a). Also, while N 2 gas containing 20% H 2 by volume was allowed to flow, the process of desorbing the stored NO 2 was measured (b).
  • initial absorption bands were shown at 1540, 1420 and 1240 cm ⁇ 1 . After 10 min, the absorption bands were greatly increased at 1440 and 1340 cm ⁇ 1 .
  • NO 2 was stored in the form of bidentate nitrate and ionic nitrite, and then was converted into ionic nitrate over time.
  • H 2 was allowed to flow to the Pt(2.0)-Cu—Cr catalyst to which NO 2 was stored, the absorption bands were rapidly decreased and then almost none thereof was seen after 15 min. This was because NO 2 stored on the catalyst by H 2 was rapidly reduced and desorbed.
  • ammonia was produced through reaction between H 2 and NO 2 .
  • the produced ammonia was strongly adsorbed on acid sites and could thus be detected using an IR spectrometer used in Example 4.
  • a mesoporous material (MCM-41) having a sulfonic acid group able to strongly adsorb ammonia was used as a test catalyst.
  • the test catalyst was fixed to the path through which IR beams were passed. While the catalyst was heated to 250° C. using a heater, H 2 was added at 30 Torr and thus reduction treatment was performed for 1 hour. After exhaust, NO 2 was fed at 20 Torr at the same temperature. Because NO 2 was not stored on acid sites, there was no difference in the test sample. Subsequently, H 2 was added at 20 Torr so that the reaction was performed for 20 min and cooling to 50° C. was performed, thus checking whether ammonia was produced.
  • FIG. 5 shows the results of the production of ammonia by adding H 2 to the Cu—Cr mixed oxide catalyst of Example 1 to which NO 2 was adsorbed, in the absence of O 2 (a) and in the presence of O 2 (b).
  • reduction treatment was performed at 250° C., after which the absorption band of sulfonic acid was greatly observed at 1377 cm ⁇ 1 .
  • the absorption band at 1377 cm ⁇ 1 became small and novel absorption bands were shown at 1440 and 1410 cm ⁇ 1 .
  • ammonia could be confirmed to be produced and adsorbed to the sulfonic acid group. While ammonia was produced and adsorbed to the sulfonic acid group, the absorption band at 1377 cm ⁇ 1 was decreased, and the absorption band of ammonium ion was shown. In the presence of O 2 , the absorption bands of ammonium ion were observed at 1440 and 1410 cm ⁇ 1 , which were smaller than in the absence of O 2 . This means that ammonia was produced through reaction between NO 2 and H 2 .
  • FIG. 6 shows IR spectra of the Cu—Mn catalyst, the Fe—Cr catalyst and the Fe—Mn catalyst, in addition to the Cu—Cr catalyst, in the presence of O 2 .
  • the absorption bands of ammonium ion were shown at 1440 and 1410 cm ⁇ 1 in the presence of O 2 , although being small.
  • the degree of production of ammonia greatly varied depending on the kind of component of the catalyst.
  • the absorption band of ammonium ion was very small.
  • the absorption band of ammonium ion was large, from which more production of ammonia could be confirmed.
  • the NO 2 reduction performance of the catalyst using a H 2 reducing agent was measured by use of a normal pressure flow reactor.
  • the construction of the flow reactor used in the H 2 -SCR reaction is shown in FIG. 7 .
  • 0.1 g of the Pt-supported catalyst was loaded in a quartz tube having an outer diameter of 10 mm and then activated at 500° C. for 1 hour.
  • cooling to 150° C. was performed, and a gas mixture of 520 ppm NO 2 by volume and 5% O 2 by volume was supplied at a flow rate of 100 ml/min and thus saturated and adsorbed to the catalyst.
  • FIG. 8 shows the results of H 2 -SCR reaction in the Pt(2.0)-Fe catalyst (a), the Pt(2.0)-Mn catalyst (b) and the Pt(2.0)-Fe—Mn catalyst (c) under conditions of 10% O 2 .
  • H 2 was supplied to the NO 2 gas at a predetermined flow rate, thus measuring the NO 2 conversion.
  • the SCR performance by H 2 in the metal oxides alone and in combinations thereof greatly varied. Specifically, in the Pt(2.0)-Fe catalyst, the reduction reaction using H 2 was barely performed at 150 ⁇ 300° C.
  • the NO 2 reduction reaction using H 2 slightly proceeded, but considerably progressed due to the injection of H 2 at 200° C., thus remarkably lowering the concentration of NO 2 .
  • part of NO 2 was desorbed because of the injection of H 2 but the reduction reaction considerably proceeded.
  • the reduction performance of the catalyst at 200 ⁇ 300° C. was evaluated to be superior to the extent that the concentration of NO 2 was close to zero.
  • the results of NO 2 reduction by injecting H 2 to the flow of NO 2 in the presence of 5% O 2 and 10% O 2 by volume are shown in Table 2.
  • the NO 2 reduction performance could be seen to greatly vary depending on the amount of supported precious metal, the kind of precious metal, and the component of mixed oxide.
  • the Pt(0.2)-Fe—Mn catalyst in which Pt was supported in an amount of 0.2% by weight exhibited the NO 2 conversion of 8 ⁇ 42% at 150 ⁇ 300° C., which was not so high.
  • the Pt(2.0)-Fe—Mn catalyst in which the amount of supported Pt was 2.0% had the NO 2 conversion of 17% at 150° C.
  • the NO 2 reduction performance was superior.
  • the effect of increasing the NO 2 conversion exceeding 100% is caused by reducing the fed NO 2 by produced ammonia, adsorbing the remaining ammonia to the surface of the catalyst or removing lattice O from the surface of the catalyst to thus additionally remove NO 2 . Because ammonia is produced from NO 2 and is used to remove NO 2 , the point of time at which H 2 is supplied does not agree with the point of time at which NO 2 is removed.
  • the NO 2 conversion was very low to the level of 2 ⁇ 17%.
  • the Pd(2.0)-Fe—Mn catalyst in which Pd was supported in place of Pt had the reduction performance similar to that of the Pt(2.0)-Fe—Mn catalyst, and thus exhibited the NO 2 conversion of 129% at 200° C. which was evaluated to be very high.
  • the Pd(2.0)-Cu—Cr catalyst exhibited the NO 2 conversion of 72% at 250° C., which was smaller than that of the Pd(2.0)-Fe—Mn catalyst but was evaluated to be high. As shown in FIG.
  • the mixed oxide catalyst for example, the Pt(2.0)-Fe—Mn catalyst, exhibiting excellent performance in the presence of 5% O 2 , was evaluated for reduction performance under an excessive O 2 content of 10%.
  • the NO 2 conversion was very low on the order of 10% or less.
  • the NO 2 conversion was considerably high on the order of 60%.
  • the NO 2 conversion exceeded 100% and the removal limitation was very low on the order of 26 ppm. Even under an excessive O 2 content of 10%, the NO 2 reduction performance was superior.
  • the reactor was packed with the Pt(2.0)-Fe—Mn catalyst having superior NO 2 reduction performance by H 2 in Table 2 and the NH 3 -SCR catalyst prepared in Example 1, for example, the Fe-BEA zeolite, and NO 2 reduction performance by H 2 was evaluated.
  • NO 2 reduction performance by H 2 was evaluated.
  • FIG. 9 shows that almost all of NO 2 was removed at 200 ⁇ 300° C. due to injection of H 2 .
  • the concentration of NO 2 was maintained low for a considerably long period of time, from which the reduction performance was evaluated to be high.
  • the reaction results are shown in Table 3 below. At 200° C., the NO 2 conversion was 133% which was evaluated to be very high.
  • the catalyst In diesel exhaust gas containing a considerable amount of water, when the temperature of exhaust gas is widely changed depending on driving conditions, the catalyst should be used without exchange for a long period of time and thus should have high hydrothermal stability. Thus, the hydrothermal stability of the mixed oxide catalyst was evaluated.
  • the precious metal-supported mixed oxide catalyst was loaded in an alumina crucible, and was placed in a quartz tube of a circular burning furnace and thus subjected to hydrothermal treatment. Then, N 2 was allowed to flow into a steam evaporator in a precision constant temperature circulator, thus preparing and supplying a gas mixture containing N 2 and 10% steam by volume. While the N 2 gas containing steam was supplied at a flow rate of 100 ml/min, the treatment was performed at 750° C. for 4 hours.
  • the catalyst was washed with water and the decrease in the activity of the mixed oxide catalyst was evaluated. 10 g of the Pt(2.0)-Fe—Mn catalyst as the Pt-supported catalyst was added to 1000 g of water, strongly stirred at room temperature, treated for 1 hour, filtered using filter paper and then dried in an oven at 80° C.
  • Adsorption Amount (mg/g) Adsorption Storage Catalyst Amount Amount Pt (2.0)—Fe—Mn 182 181 Pt (2.0)—Fe—Mn (Water Treatment) 72 66 Pt (2.0)—Fe—Mn (Hydrothermal Treatment) 84 82
  • the amount of NO 2 stored on the Pt(2.0)-Fe—Mn catalyst subjected to water treatment and hydrothermal treatment is shown in Table 4.
  • the amount of stored NO 2 through water treatment and hydrothermal treatment was lowered from 181 mg/g to 66 mg/g and 82 mg/g respectively.
  • the amount of stored NO 2 was considerably lowered through hydrothermal treatment.
  • Table 5 below shows the results of NO 2 reduction by H 2 in the Pt-supported Fe—Mn catalyst subjected to water treatment and hydrothermal treatment.
  • the reduction performance of the Pt(2.0)-Fe—Mn catalyst subjected to water treatment was similar to that before the treatment.
  • the removal performance was slightly decreased at high temperatures, but was greatly increased at low temperatures.
  • the NO 2 conversion and the H 2 efficiency at 150° C. were 17% and 2% respectively, and thus the removal performance was poor.
  • the NO 2 conversion and the H 2 efficiency were considerably increased to 73% and 10% respectively, but were slightly decreased at 250 ⁇ 300° C.
  • the NO 2 reduction performance at 150 ⁇ 200° C. was considerably deteriorated, and was greatly improved at temperatures not lower than 250° C.
  • the Pt(2.0)-Fe—Mn catalyst exhibited had the NO 2 conversion and the H 2 efficiency of 89% and 12% respectively at 300° C., and the NO 2 conversion and the H 2 efficiency of the Pt(2.0)-Fe—Mn catalyst subjected to hydrothermal treatment were considerably improved to 121% and 16% respectively.
  • the diesel exhaust gas contains sulfur compounds including SO 2 , undesirably deteriorating the activity of the catalyst.
  • the catalyst was poisoned with SO 2 .
  • the catalyst was exhausted, activated and then sufficiently poisoned with SO 2 gas at 10 Torr at 150° C. for 1 hour, before storing NO 2 . After exhaust for 1 hour, NO 2 at 30 Torr was supplied and thus the adsorption amount thereof was measured.
  • the amount of adsorbed SO 2 and the amount of stored NO 2 after poisoning are shown in Table 6 below. At 150° C., SO 2 was not adsorbed in a large amount. Upon treatment with SO 2 , the amount of stored NO 2 was decreased by almost half.
  • the NO 2 removal performance by H 2 after sulfur poisoning is shown in Table 7 below.
  • the NO 2 reduction performance of the Pt(2.0)-Fe—Mn catalyst poisoned with SO 2 was almost the same as that before sulfur poisoning.
  • the NO 2 conversion and the H 2 efficiency were slightly decreased, but the NO 2 removal limitation at 200° C. was 35 ppm which was equivalent to that before sulfur poisoning.

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KR20230146242A (ko) 2022-04-12 2023-10-19 한국화학연구원 수소를 이용한 선택적 촉매환원 반응용 저온 탈질촉매 및 그 제조방법
EP4282513A1 (fr) * 2022-05-23 2023-11-29 Basf Corporation Catalyseurs améliorés pour la réduction sélective de nox à l'aide d'hydrogène
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US9511350B2 (en) 2013-05-10 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) ZPGM Diesel Oxidation Catalysts and methods of making and using same
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US9511355B2 (en) 2013-11-26 2016-12-06 Clean Diesel Technologies, Inc. (Cdti) System and methods for using synergized PGM as a three-way catalyst
US20160129425A1 (en) * 2014-11-10 2016-05-12 Toyota Jidosha Kabushiki Kaisha Exhaust gas purifying catalyst for selective reduction of nox and exhaust gas purifying method
JP2016087587A (ja) * 2014-11-10 2016-05-23 トヨタ自動車株式会社 ＮＯｘ選択還元用排ガス浄化触媒及び排ガス浄化方法
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US10717074B2 (en) 2016-06-21 2020-07-21 Haldor Topsoe A/S Method for preparation of a monolithic catalyst for the reduction of nitrogen oxides, VOC and carbon monoxide in an off-gas
CN108772057A (zh) * 2018-06-28 2018-11-09 广东工业大学 一种低温scr氧化锰催化剂及其制备方法和应用
JPWO2020179891A1 (fr) * 2019-03-07 2020-09-10
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CN115245827A (zh) * 2021-12-17 2022-10-28 中国石油天然气股份有限公司 一种共沉淀-浸渍制备一氧化二氮分解催化剂的方法

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WO2010013856A3 (fr) 2010-07-15
KR100962082B1 (ko) 2010-06-09
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