WO2024035057A1 - Catalyseur de traitement d'émission comprenant une zéolite et de l'oxyde métallique - Google Patents

Catalyseur de traitement d'émission comprenant une zéolite et de l'oxyde métallique Download PDF

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WO2024035057A1
WO2024035057A1 PCT/KR2023/011649 KR2023011649W WO2024035057A1 WO 2024035057 A1 WO2024035057 A1 WO 2024035057A1 KR 2023011649 W KR2023011649 W KR 2023011649W WO 2024035057 A1 WO2024035057 A1 WO 2024035057A1
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catalyst
emission treatment
reactor
zeolite
ammonia
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Korean (ko)
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김기왕
김진홍
안지혜
김동우
김정배
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주식회사 에코프로에이치엔
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B01D2255/2047—Magnesium
    • 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
    • B01D2255/20753—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • 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

Definitions

  • the present invention relates to effluent treatment catalysts comprising zeolites and metal oxides. Specifically, the present invention relates to an exhaust treatment catalyst comprising a first catalyst and a second catalyst, wherein the first catalyst is a zeolite catalyst and the second catalyst is a catalyst obtained by adding nickel and magnesium to alumina.
  • process emissions mainly include volatile organic compounds (VOC) and odor-causing compounds.
  • VOC volatile organic compounds
  • Process emissions containing organic volatile substances and odor-causing substances are a cause of air pollution, and therefore treatment technologies for organic volatile substances and odor-causing substances are required.
  • organic volatile substances are treated by means such as regenerative thermal oxidation or regenerative catalytic oxidation.
  • Low concentrations of organic volatile substances are concentrated and then treated using a concentrator (e.g., a rotating rotor containing an adsorbent) to increase treatment efficiency.
  • a concentrator e.g., a rotating rotor containing an adsorbent
  • the regenerative thermal oxidation method can be an economical method, but when the reaction temperature is too high to increase treatment efficiency, there is a problem in that NO x is generated and secondary pollutants are emitted.
  • ammonia among odor-causing substances, is easily soluble in water, so exhaust gas containing ammonia is treated by washing with water.
  • ammonia can be treated by dissolving it in water or an aqueous solution containing specific chemicals designed to increase the solubility of ammonia, but considering that regulations on total nitrogen content are becoming stricter in terms of water quality environment, inside the workplace Alternatively, secondary treatment is required externally, such as wet oxidation.
  • nitrogen oxides for example, NO A reducing agent such as urea solution must be additionally used. At this time, a separate de- NO
  • organic volatile substances substances soluble in water (e.g., alcohols, ketones, aldehydes, etc.) can be removed by washing with water and using a wet oxidation method.
  • wet oxidation methods are used. It can be treated by dissolving it in water or an aqueous solution containing chemicals to increase the solubility of water-soluble organic volatile substances and ammonia, but secondary pollution sources may occur.
  • wet abatement methods e.g., wet scrubbers
  • wastewater treatment e.g., wet oxidation
  • the present inventor completed the present invention after continuous research on a catalyst that can effectively treat not only primary pollutants such as organic volatile substances and odor-causing substances but also secondary pollutants such as nitrogen oxides through oxidation or reduction reactions.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2020-0130845
  • Patent Document 2 Republic of Korea Patent Publication No. 10-2022-0057376
  • the present invention provides an emission treatment catalyst that has high durability in treating emissions such as organic volatile substances and odor-causing substances and has high selectivity in converting pollutants into an emissible form such as nitrogen and carbon dioxide.
  • the present invention provides an exhaust treatment catalyst in which a first catalyst and a second catalyst are introduced on a support, wherein the first catalyst is a zeolite catalyst and the second catalyst is a catalyst obtained by adding nickel and magnesium to alumina. do.
  • the support is a honeycomb structure made of ceramic material, and the ceramic material includes at least one of cordierite, silica, and titania.
  • the zeolite catalyst is ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-23, MCM-zeolite, mordenite, posersite, ferrierite, zeolite beta, It is selected from the group consisting of chabazite and mixtures thereof.
  • the zeolite catalyst is a metal ion-exchanged zeolite catalyst, and the metal ion is Fe, Cu, or a combination thereof.
  • the total content of nickel and magnesium in the second catalyst is 20 to 40 parts by weight based on 100 parts by weight of alumina.
  • the weight ratio of nickel and magnesium in the second catalyst is 5:1 to 15:1.
  • the weight ratio of the first catalyst and the second catalyst in the exhaust treatment catalyst is 1:1 to 9:1.
  • the first catalyst and the second catalyst are mixed and introduced into one or more coating layers.
  • the first catalyst and the second catalyst are introduced separately as separate coating layers.
  • the exhaust treatment catalyst includes a structure in which a first coating layer including a first catalyst is coated on a support, and a second coating layer including a second catalyst is coated on the first coating layer. do.
  • the first catalyst is introduced in an amount of 50 g/L to 150 g/L based on the total exhaust treatment catalyst.
  • the second catalyst is introduced in an amount of 20 g/L to 80 g/L based on the total exhaust treatment catalyst.
  • the emission treatment catalyst according to the present invention includes a zeolite catalyst as a first catalyst and a catalyst obtained by adding nickel and magnesium to alumina as a second catalyst, thereby treating emissions of various components such as organic volatile substances, odor-causing substances, etc. It has a long lifespan due to the excellent durability of the catalyst, and has high utility value in related industrial fields due to its high selectivity in converting pollutants into exudable forms such as nitrogen and carbon dioxide.
  • Figure 1a is a diagram schematically showing the structure of an emission treatment catalyst according to an embodiment of the present invention.
  • Figure 1b is a diagram schematically showing the structure of an emission treatment catalyst according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of an exemplary process in which an effluent treatment catalyst according to one embodiment of the present invention may be utilized.
  • Figure 3a is an overall SEM image of the catalyst of Example 1 according to Experimental Example 1
  • Figure 3b is an SEM image of each component of a portion of Figure 3a.
  • Figure 4a is an overall SEM image of the catalyst of Example 2 according to Experimental Example 1
  • Figure 4b is an SEM image of each component of a portion of Figure 4a.
  • Figure 5a is an overall SEM image of the catalyst of Example 3 according to Experimental Example 1
  • Figure 5b is an SEM image of each component of a portion of Figure 5a.
  • Figure 6a is an overall SEM image of the catalyst of Example 4 according to Experimental Example 1
  • Figure 6b is an SEM image of each component of a portion of Figure 6a.
  • Figure 7a is a graph showing the results of measuring the emissions (ppm) of isopropanol and CO for the catalyst of Comparative Example 2 according to Experimental Example 2.
  • Figure 7b is a graph showing the results of measuring the emissions (ppm) of isopropanol and CO for the catalyst of Comparative Example 3 according to Experimental Example 2.
  • Figure 8 is a graph showing the results of measuring catalyst durability (k/k 0 value) for each of the catalyst of Comparative Example 1, the catalyst of Example 1, and the catalyst of Example 2 according to Experimental Example 3.
  • Figure 9a is a graph showing the concentration of each component by day in flow c of Experimental Example 5.
  • Figure 9b is a graph showing the concentration of each component by day in flow d of Experimental Example 5.
  • the present invention provides an exhaust treatment catalyst incorporating a first catalyst and a second catalyst on a support.
  • the catalyst is a catalyst that can be used in general oxidation or reduction reactions of organic or inorganic compounds. Specifically, it oxidizes or reduces process emissions of organic or inorganic compounds emitted from specific industrial fields such as semiconductor and display processes to water, nitrogen, etc. And it can be used in the process of processing it into an emissible form such as carbon dioxide. These emissions include primary pollutants such as organic volatile substances and odor-causing substances, and the catalyst can be suitably used to oxidize or reduce these primary pollutants. In addition, the catalyst can be suitably used to oxidize or reduce secondary pollutants that may be generated during the treatment of primary pollutants as well as the treatment of primary pollutants.
  • the primary or secondary pollutants include, for example, ammonia (NH 3 ), nitrogen oxides (for example, NO x (NO, NO 2 ) or N 2 O, etc.), or organic volatiles such as isopropanol (IPA). It can be a substance.
  • the catalyst is used for a simultaneous oxidation reaction of ammonia and organic volatile substances, or a selective reduction reaction of nitrogen oxides, etc.
  • the emission treatment catalyst according to the present invention may be in the form of a first catalyst and a second catalyst introduced onto a support.
  • the support has the function of supporting and fixing the first catalyst and the second catalyst, and is not particularly limited as long as it is a material commonly used in the relevant technical field.
  • the support may have a honeycomb structure and may be made of a ceramic material containing at least one of cordierite, silica, and titania. Specifically, the ceramic material may be cordierite.
  • the first catalyst introduced into the support is a substance that affects the reaction rate during the oxidation or reduction of primary pollutants included in the discharge or secondary pollutants that may be generated during the treatment of the primary pollutants. It helps secondary pollutants to ultimately be converted into non-emissionable non-pollutants such as water, nitrogen, and carbon dioxide.
  • the first catalyst is not particularly limited as long as it is a material having the above-described functionality.
  • the first catalyst is a zeolite catalyst.
  • the zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-23, MCM-zeolite, mordenite, faujasite, ferrierite, and beta.
  • the first catalyst has a ratio of 500 m2/g to 800 m2/g, specifically 525 m2/g to 750 m2/g, more specifically 550 m2/g to 700 m2/g. It has a surface area. The specific surface area is measured by the BET method.
  • the zeolite catalyst is a metal ion-exchanged zeolite catalyst.
  • the type of the metal ion is not particularly limited as long as it is a metal ion that can be generally introduced into zeolite catalysts in the relevant technical field.
  • the metal ion is Fe, Cu, or a combination thereof.
  • the metal ion is 0.1% by weight to 10% by weight, specifically 0.5% by weight to 7.5% by weight, more specifically 1% by weight to 5% by weight based on the total weight of the catalyst. is introduced in
  • the second catalyst introduced into the support is a substance that affects the reaction rate when oxidizing or reducing primary pollutants included in the discharge or secondary pollutants that may be generated during the treatment of the primary pollutants. , helps primary or secondary pollutants to be finally converted into non-polluting sources that can be discharged, such as water, nitrogen, and carbon dioxide.
  • the second catalyst is not particularly limited as long as it is a material having the above-mentioned functionality.
  • the second catalyst is a catalyst obtained by adding nickel (Ni) and magnesium (Mg) to alumina (Al 2 O 3 ).
  • the second catalyst has a ratio of 50 m2/g to 250 m2/g, specifically 75 m2/g to 200 m2/g, more specifically 100 m2/g to 150 m2/g. It has a surface area. The specific surface area is measured by the BET method.
  • the first catalyst and the second catalyst individually have excellent functionality in treating effluents, but when the types of pollutants vary, the functionality of the first catalyst or the second catalyst deteriorates, which reduces the functionality of the entire catalyst. may lead to degradation.
  • the first catalyst and the second catalyst are selected as a combination that does not deteriorate the functionality of the overall catalyst even if there are various types of contaminants.
  • the emission treatment catalyst according to the present invention can be preferably used for the simultaneous treatment of ammonia and organic volatile substances as well as the treatment of nitrogen oxides.
  • the first catalyst is 50 g/L to 150 g/L, specifically 65 g/L to 135 g/L, more specifically 80 g/L, based on the total effluent treatment catalyst.
  • the second catalyst is 20 g/L to 80 g/L, specifically 25 g/L to 75 g/L, more specifically 30 g/L, based on the total effluent treatment catalyst. to 70 g/L are introduced.
  • the weight ratio of the first catalyst and the second catalyst in the exhaust treatment catalyst is 1:1 to 9:1, specifically 1:1 to 6:1, more specifically 1:1 to 4. :1. Within the above-mentioned range, the effect of using the first catalyst and the second catalyst in combination may be more highlighted.
  • the zeolite catalyst used as the first catalyst is selective for ammonia (SCO reaction) and partially oxidized nitrogen oxides (NO x ) and ammonia. It may be suitable for catalytic reduction reaction (SCR reaction), and the catalyst with nickel and magnesium added to alumina used as a second catalyst is suitable for the production of nitrogen oxides by partial oxidation of ammonia and the oxidation reaction of organic volatile substances such as isopropanol. can do.
  • the second catalyst has resistance to coke, so the performance of the catalyst can be maintained for a long time when treating organic volatile substances.
  • the oxidizing power of the catalyst may be insufficient.
  • the oxidizing power of the catalyst is increased by mixing noble metals such as palladium (Pd) and platinum (Pt).
  • Pd palladium
  • Pt platinum
  • a complete oxidation reaction may occur for organic volatile substances, but for ammonia, the selectivity (or conversion rate) to nitrogen may be significantly reduced, which may be undesirable.
  • the second catalyst a catalyst in which nickel and magnesium are added to alumina, is used alone, it may be possible to use it alone, but it is preferable because the selectivity (or conversion rate) for ammonia to nitrogen is not high compared to the zeolite catalyst. You may not.
  • the second catalyst is basically an alumina-based catalyst and contains both nickel and magnesium as essential components.
  • nickel and magnesium may exhibit oxidizing properties
  • magnesium may exhibit reducing properties.
  • nickel can be decomposed by oxidizing isopropanol adsorbed on the catalyst surface. In this case, the formation of coke on the catalyst surface due to incomplete oxidation can be prevented through the reducing properties of magnesium.
  • NH 3 can generate some NO x by NiMg-Al 2 O 3 , and at this time , the generated NO It can be converted to 2 .
  • the total content of nickel and magnesium in the second catalyst is 20 parts by weight to 40 parts by weight, specifically 23 parts by weight to 36 parts by weight, more specifically 26 parts by weight, based on 100 parts by weight of alumina. to 32 parts by weight.
  • the effects of adding nickel and magnesium may be more prominent.
  • nickel can be added to alumina in a much larger amount than magnesium.
  • the weight ratio of nickel and magnesium in the second catalyst is 5:1 to 15:1, specifically 6.5:1 to 13.5:1, and more specifically 8:1 to 12:1. Within the above-mentioned range, the effects of adding nickel and magnesium may be more prominent.
  • FIG. 1A and 1B show a schematic structure of an exhaust treatment catalyst according to one embodiment of the present invention.
  • Figures 1a and 1b are intended to briefly explain the structure into which the first and second catalysts are introduced, focusing on the surface of the support, and the structures shown in Figures 1a and 1b do not represent the entire structure of the catalyst. .
  • the first catalyst and the second catalyst are mixed and introduced into one or more coating layers, and the structure of the catalyst follows FIG. 1A.
  • the first catalyst and the second catalyst are introduced separately as separate coating layers, and the structure of these catalysts follows Figure 1b.
  • the order of the coating layer containing the first catalyst and the coating layer containing the second catalyst is not particularly limited, but after coating the first coating layer containing the first catalyst on the support, the second coating layer containing the second catalyst is applied. When coated, the durability of the catalyst against coke generated when treating carbon-based compounds such as organic volatile substances increases, which may be advantageous for its lifespan.
  • the exemplary process is a simultaneous reduction of isopropanol and ammonia, the process comprising: (1) supplying industrial exhaust gas containing isopropanol and ammonia to a first reactor; (2) oxidizing isopropanol and ammonia in the first reactor; (3) supplying the discharge from the first reactor to a second reactor; (4) producing nitrogen, carbon dioxide, and water in the second reactor; and (5) discharging the effluent from the second reactor.
  • step (1) industrial exhaust gas containing isopropanol and ammonia is first supplied to the first reactor.
  • concentration of isopropanol and ammonia in industrial exhaust gas it is desirable for the concentration of isopropanol and ammonia in industrial exhaust gas to be above a certain level.
  • the sum of the concentrations of isopropanol and ammonia in industrial exhaust gas is 100 ppm to 10,000 ppm, specifically 2,000 ppm to 9,000 ppm, more specifically 4,000 ppm to 8,000 ppm, and the concentration of isopropanol is 10% based on the concentration of ammonia.
  • the concentrations of isopropanol and ammonia may each be 100 ppm or more, specifically 1,000 ppm or more, and more specifically 2,000 ppm or more. If the concentration of either isopropanol or ammonia is too low, the interference between the two components is minimal, and a similar effect can be achieved through an invention designed to remove either component, which may reduce the effectiveness of the process alone. there is. On the contrary, if the concentration of either isopropanol or ammonia is too high, excellent effects cannot be achieved through the process, and the effectiveness of the process may be reduced.
  • the process includes a selective oxidation reaction of ammonia (i.e., a reaction in which ammonia is selectively oxidized to nitrogen (N 2 ) and water (H 2 O) under specific conditions or on a catalyst), where the concentration of isopropanol is excessive.
  • a selective oxidation reaction of ammonia i.e., a reaction in which ammonia is selectively oxidized to nitrogen (N 2 ) and water (H 2 O) under specific conditions or on a catalyst
  • the concentration of isopropanol is excessive.
  • the concentration of isopropanol is too high, the reaction heat generated during the oxidation treatment of isopropanol can cause ammonia to be removed.
  • the oxidation reaction is also activated and a large amount of NO x (i.e. NO or NO 2 ) is generated, the purpose of the process cannot be achieved without a separate reducing agent supply step.
  • the sum of the concentrations of isopropanol and ammonia described above is at a level that can increase treatment efficiency when applied to actual industrial fields. If the concentration of isopropanol and ammonia in the supplied industrial exhaust gas is low, a concentrator capable of adsorbing isopropanol and ammonia can be used to control the concentration of isopropanol and ammonia before feeding it to the first reactor.
  • the supply flow rate is separated into a first flow rate and a second flow rate, and the first flow rate is supplied to the first reactor, and the second flow rate is supplied to the first reactor.
  • the flow rate may be mixed with the effluent from the first reactor.
  • the ammonia contained in the second flow rate in the second reactor decomposes NO x or N 2 O. It can be used as a reducing agent to increase reaction efficiency.
  • the distribution of the first flow rate and the second flow rate can be determined by the following calculation equation 1.
  • Q a means the supply flow rate before distribution
  • Q a2 means the second flow rate
  • f is related to the amount of NO x discharged from the first reactor (c ) , the amount of ammonia required to completely remove the equivalent amount of NO It can be defined as the amount (a) of ammonia that must be introduced into the second reactor to remove NO there is. This is summarized in the following calculation formula 2.
  • a is calculated by c ⁇ d ⁇ x.
  • c refers to the amount of NO x discharged from the first reactor, and is determined by adding the amount of NO (c 1 ) and the amount of NO 2 (c 2 ).
  • d means the equivalent amount of ammonia required to completely remove 1 equivalent amount of NO x refers to the desired removal efficiency of NO x , and is determined in advance taking into account the concentrations of isopropanol, ammonia, and NO x can be set to 0.5 to 1.5, specifically 0.6 to 1.4, and more specifically 0.7 to 1.3. If the x value is smaller than the above range, the reduction efficiency of NO This may deteriorate.
  • emissions of secondary pollutants such as NO x and N 2 O can be minimized.
  • the feed flow of industrial exhaust gases (if separated, the first flow) is fed to a first reactor, in which isopropanol and ammonia are oxidized.
  • Oxidation of isopropanol and ammonia is the reaction of isopropanol and ammonia with oxygen, respectively, whereby the following reactions can be performed.
  • Schemes 1 and 2 are the main reactions targeted in the first reactor, and Schemes 3 to 8 are side reactions that may occur during the actual reaction.
  • isopropanol and ammonia are oxidized at the same time, since the reaction cannot be performed under optimal conditions for each reactant, a certain level of side reactions are inevitably accompanied. To remove secondary contaminants caused by these side reactions, additional reactions are required.
  • Oxygen which is a reactant other than isopropanol and ammonia, is generally contained in a sufficient amount in the exhaust gas, but additional air can be supplied to the reactor as needed.
  • isopropanol and ammonia may be oxidized by a catalyst.
  • Figure 2 shows an exemplary process diagram when the first reactor is a catalytic oxidation reactor.
  • the first reactor is equipped with a catalyst in the form of a fixed bed catalytic reactor. At this time, it may be desirable to select a catalyst that has oxidation reaction performance and is effective in the selective oxidation reaction of NH 3 and NH 3 -deNO x reaction, and is not particularly limited as long as the catalyst has such functionality.
  • the effluent treatment catalyst according to the present invention can be preferably applied to the first reactor.
  • the first reactor which is a catalytic oxidation reactor, may be operated under temperature conditions of 100°C to 650°C, specifically 200°C to 600°C, and more specifically 300°C to 550°C. If the temperature is lower than the corresponding range, the overall oxidation reaction does not proceed actively, which is undesirable, and if the temperature is higher than the corresponding range, excessive NO x is generated, which is undesirable.
  • the first reactor may be operated under pressure conditions of atmospheric pressure to 10 atmospheres, specifically atmospheric pressure to 7 atmospheres, and more specifically atmospheric pressure to 5 atmospheres. At high pressures, device costs may increase because pressure-resistant vessels must be adopted.
  • the first reactor may be operated under gas space velocity (GHSV) conditions of 200hr -1 to 20,000hr -1 , specifically, 500hr -1 to 10,000hr -1 , and more specifically 1,000hr -1 to 5,000hr -1 there is. If the gas space velocity is lower than the corresponding range, it is undesirable because the device must be enlarged, and if the gas space velocity is higher than the corresponding range, it is undesirable because the efficiency and selectivity of the reaction decreases.
  • GHSV gas space velocity
  • the catalytic oxidation reactor may be designed so that the ratio of ammonia in the reactant converted to nitrogen oxides ( NO there is.
  • the discharge from the first reactor is fed to the second reactor.
  • the second flow rate is mixed with the discharge from the first reactor and supplied to the second reactor.
  • Nitrogen, carbon dioxide and water are mainly produced in the second reactor.
  • the following reactions can mainly be performed in the second reactor.
  • Schemes 9 to 11 are the main reactions targeted in the second reactor, and Schemes 12 to 14 are side reactions that may occur during the actual reaction.
  • the NO x component generated in the first reaction reacts with ammonia and is decomposed into nitrogen and water.
  • the NO it may be desirable to select a catalyst that has oxidation reaction performance and is effective in NH 3 -deN 2 O and NH 3 -deNO x reactions, and is not particularly limited as long as the catalyst has such functionality.
  • the effluent treatment catalyst according to the present invention can be preferably applied to the second reactor.
  • the second reactor may be operated under temperature conditions of 100°C to 650°C, specifically 150°C to 600°C, and more specifically 200°C to 550°C. If the temperature is lower than that range, it is not desirable because the overall oxidation reaction does not proceed actively, and if the temperature is higher than that range, the oxidation reaction of ammonia proceeds competitively with the de-NO x reaction, resulting in excessive NO x generation. Therefore, it is not desirable.
  • the first reactor may be operated under pressure conditions of atmospheric pressure to 10 atmospheres, specifically atmospheric pressure to 7 atmospheres, and more specifically atmospheric pressure to 5 atmospheres. At high pressures, device costs may increase because pressure-resistant vessels must be adopted.
  • the second reactor may be operated under gas space velocity (GHSV) conditions of 200hr -1 to 20,000hr -1 , specifically 500hr -1 to 15,000hr -1 , and more specifically 1,000hr -1 to 10,000hr -1 . If the gas space velocity is lower than the corresponding range, it is undesirable because the device must be enlarged, and if the gas space velocity is higher than the corresponding range, it is undesirable because the efficiency and selectivity of the reaction decreases.
  • GHSV gas space velocity
  • NiMg-Al 2 O 3 (name) was prepared.
  • the specific components of the catalyst are shown in Table 1 below.
  • NiMg-Al 2 O 3 is a catalyst in which nickel and magnesium are added to alumina, and the contents of the added nickel and magnesium are according to Table 1 below.
  • catalyst 1 catalyst 2 catalyst 3 Cu content (wt%) 3 ⁇ 4 - - Fe content (wt%) - 1 ⁇ 2 - Ni content (wt%) - - 20 Mg content (wt%) - - 2 SiO 2 content (wt%) 86.4 92.8 - Al 2 O 3 content (wt %) 9.9 5.1 78 SiO 2 /Al 2 O 3 15 ⁇ 18 30 ⁇ 40 - Specific surface area (m2/g) 500 ⁇ 650 550 ⁇ 700 100 ⁇ 150
  • Pt-Al 2 O 3 (hereinafter referred to as 'Catalyst 4'), Pd-Al 2 O 3 (hereinafter referred to as 'Catalyst 5'), and Pt/Fe_beta zeolite (hereinafter referred to as 'Catalyst 5') (referred to as 'Catalyst 6') was prepared.
  • the specific components of the catalyst are shown in Table 1 below.
  • Pt-Al 2 O 3 is a catalyst in which platinum is added to alumina
  • Pd-Al 2 O 3 is a catalyst in which palladium is added to alumina
  • Pt/Fe_beta zeolite is a catalyst in which platinum is added to Fe_beta zeolite. It is an added catalyst.
  • the content of added platinum or palladium follows Table 2 below.
  • a mixture was prepared by mixing the first catalyst, Catalyst 1 (Cu_chabazite), and the second catalyst, Catalyst 3 (NiMg-Al 2 O 3 ) in a 1:1 weight ratio, and then placed on a honeycomb-structured cordierite support. The mixture was coated at approximately 150 g/L per volume of cordierite. Afterwards, the catalyst was finally prepared by calcining at 550°C for 4 hours.
  • Catalyst 1 Cu_chabazite
  • Catalyst 3 NiMg-Al 2 O 3
  • Catalyst 2 Fe_beta zeolite
  • Catalyst 3 NiMg-Al 2 O 3
  • Catalyst 1 (Cu_chabazite) was used as is.
  • Catalyst 2 (Fe_beta zeolite) was used as is.
  • Catalyst 3 (NiMg-Al 2 O 3 ) was used as is.
  • Catalyst 4 (Pt-Al 2 O 3 ) was used as is.
  • Catalyst 5 (Pd-Al 2 O 3 ) was used as is.
  • Catalyst 6 (Pt/Fe_beta zeolite) was used as is.
  • Figures 3a and 3b are SEM images of the catalyst of Example 1. According to Figures 3a and 3b, it can be seen that Cu and Si are coated on the inside, and Ni, Mg, and Al are coated on the outside.
  • Figures 4a and 4b are SEM images of the catalyst of Example 2. According to Figures 4a and 4b, it can be seen that Ni, Cu, etc. are mixed and coated.
  • Figures 5a and 5b are SEM images of the catalyst of Example 3. According to Figures 5a and 5b, it can be seen that Fe and Si are coated on the inside, and Ni, Mg, and Al are coated on the outside.
  • Figures 6a and 6b are SEM images of the catalyst of Example 4. According to Figures 6a and 6b, it can be seen that Ni, Fe, etc. are mixed and coated.
  • Stream a passing through the concentrator 20 had a total flow rate of 1 L/min, where isopropanol and ammonia each had a concentration of 3,000 ppm.
  • the stream a was supplied to the first reactor without a separate bypass stream (a2).
  • the first reactor was a fixed bed catalyst reactor, and the temperature was changed while the pressure of 1.5 atm and gas space velocity (GHSV) of 15,000 hr -1 were fixed, and the degree of oxidation of isopropanol was evaluated.
  • GHSV gas space velocity
  • Stream a passing through the concentrator 20 had a total flow rate of 1 L/min, where isopropanol and ammonia each had a concentration of 3,000 ppm.
  • the stream a was supplied to the first reactor without a separate bypass stream (a2).
  • the first reactor was a fixed bed catalytic reactor operated at a pressure of 1.5 atm, a gas space velocity (GHSV) of 15,000 hr -1 , and a reaction temperature of 530°C.
  • GHSV gas space velocity
  • Stream a passing through concentrator 20 had a total flow rate of 5 L/min, where isopropanol and ammonia each had a concentration of 3,000 ppm.
  • the flow a was divided into flow a 1 with a flow rate of 0.85 L/min and flow a 2 with a flow rate of 0.15 L/min, and flow a 1 was supplied to the first reactor.
  • the first reactor was a fixed bed catalytic reactor and was operated while changing the temperature while maintaining a fixed pressure of 1.5 atm and a gas space velocity (GHSV) of 3,000 hr -1 .
  • the catalysts used were the catalyst of Example 1, the catalyst of Example 2, the catalyst of Example 3, the catalyst of Example 4, the catalyst of Comparative Example 3, the catalyst of Comparative Example 4, the catalyst of Comparative Example 5, and the catalyst of Comparative Example 6. Each was charged.
  • the stream b joined the distributed stream a2 before being fed to the first reactor and stream c was fed to the second reactor.
  • the second reactor was a fixed bed catalytic reactor operated at a pressure of 1.5 atm, a gas space velocity (GHSV) of 6,000 hr -1 and a reaction temperature of 450°C.
  • the catalyst was first coated with Fe-BEA catalyst powder, in which 2% Fe was ion-exchanged to BEA ( ⁇ -zeolite), on a 100cpsi (cells per square inch) honeycomb support made of cordierite, and 1.5% by weight of Cobalt-magnesium-alumina catalyst powder containing cobalt and 2% by weight of magnesium was secondarily coated.
  • the weight ratio of the Fe-BEA catalyst and the cobalt-magnesium-alumina catalyst was adjusted to be 9:1, and the sum of the coating amounts of each catalyst was adjusted to be 150 g/L.
  • Example 1 Temperature (°C) Conversion rate of NH 3 (%) Conversion rate of NH 3 to N 2 (%) IPA conversion rate (%) CO concentration (ppm) 400 100.0 94.8 99.90 141 430 100.0 91.5 99.97 74 450 100.0 90.3 99.97 51 500 100.0 81.8 99.98 38
  • Example 1 the catalyst of Example 1 or the catalyst of Example 2, which introduced Catalyst 1 (Cu_chabazite) and Catalyst 3 (NiMg-Al 2 O 3 ) on cortierite, was used.
  • Catalyst 1 Cu_chabazite
  • Catalyst 3 NiMg-Al 2 O 3
  • CO concentration it can be seen that both catalysts of Examples 1 and 2 begin to drop below 100 ppm around 430°C.
  • flow c supplied to the second reactor had a total flow rate of 1 L/min, and each component had the same concentration as shown in Figure 9a for each day.
  • the second reactor was a fixed bed catalytic reactor operated at a pressure of 1.5 atm, a gas space velocity (GHSV) of 6,000 hr -1 and a reaction temperature of 450°C.
  • the catalyst of Example 1 was charged as a catalyst.
  • the concentration of each component of the stream d discharged from the second reactor is shown in Figure 9b.
  • 1B Single coating layer of first or second catalyst (including a different catalyst than 1A)

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Abstract

La présente invention concerne un catalyseur de traitement d'émission dans lequel un premier catalyseur et un second catalyseur sont introduits sur un support. Le premier catalyseur représente un catalyseur de zéolite, et le second catalyseur représente un catalyseur dans lequel du nickel et du magnésium sont ajoutés à de l'alumine. Le premier catalyseur et le second catalyseur peuvent être mélangés et introduits en tant qu'une ou plusieurs couches de revêtement, ou peuvent également être introduits en tant que couches de revêtement respectives séparées. En comprenant le premier catalyseur et le second catalyseur, le catalyseur de traitement d'émission selon la présente invention présente une longue durée de vie en raison d'une excellente durabilité de celui-ci même lorsqu'il est utilisé pour traiter les émissions de divers composants, tels que des composés organiques volatils et des composés provoquant une odeur, et présente une sélectivité élevée pour convertir des polluants en une forme qui peut être émise, telle que l'azote, le dioxyde de carbone, ou similaire, et est ainsi hautement utilisé dans les industries associées.
PCT/KR2023/011649 2022-08-09 2023-08-08 Catalyseur de traitement d'émission comprenant une zéolite et de l'oxyde métallique WO2024035057A1 (fr)

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