KR20240007879A - Catalyst for combustion of carbon particulate matter using rhodium and silver impregnated on macroporous ceria support, and method for carbon particulate matter combustion using the same - Google Patents
Catalyst for combustion of carbon particulate matter using rhodium and silver impregnated on macroporous ceria support, and method for carbon particulate matter combustion using the same Download PDFInfo
- Publication number
- KR20240007879A KR20240007879A KR1020230086787A KR20230086787A KR20240007879A KR 20240007879 A KR20240007879 A KR 20240007879A KR 1020230086787 A KR1020230086787 A KR 1020230086787A KR 20230086787 A KR20230086787 A KR 20230086787A KR 20240007879 A KR20240007879 A KR 20240007879A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- combustion
- silver
- rhodium
- supported
- Prior art date
Links
- 239000010948 rhodium Substances 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 52
- 239000004332 silver Substances 0.000 title claims abstract description 52
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 50
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000013618 particulate matter Substances 0.000 title abstract description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 50
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 20
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012695 Ce precursor Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009841 combustion method Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000011236 particulate material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- -1 and at the same time Substances 0.000 description 4
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QKLCKVVKVHCMIC-UHFFFAOYSA-N rhodium(3+);trinitrate;hydrate Chemical compound O.[Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QKLCKVVKVHCMIC-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- AHGQVCBMBCKNFG-KJVLTGTBSA-N cerium;(z)-4-hydroxypent-3-en-2-one;hydrate Chemical compound O.[Ce].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O AHGQVCBMBCKNFG-KJVLTGTBSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910004755 Cerium(III) bromide Inorganic materials 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910008069 Cerium(III) iodide Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- POAMYEHCTFMTGA-UHFFFAOYSA-L [F-].[Ce+4].[F-].[Ce+4] Chemical compound [F-].[Ce+4].[F-].[Ce+4] POAMYEHCTFMTGA-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- GGVUYAXGAOIFIC-UHFFFAOYSA-K cerium(3+);2-ethylhexanoate Chemical compound [Ce+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GGVUYAXGAOIFIC-UHFFFAOYSA-K 0.000 description 1
- WSVMKOQJZBJDJB-UHFFFAOYSA-H cerium(3+);oxalate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O WSVMKOQJZBJDJB-UHFFFAOYSA-H 0.000 description 1
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 description 1
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- KKVSNHQGJGJMHA-UHFFFAOYSA-H cerium(3+);trisulfate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KKVSNHQGJGJMHA-UHFFFAOYSA-H 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/005—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—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
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
본 발명은 대형 기공 구조를 갖는 세륨 산화물 지지체에 로듐 및 은을 담지한 탄소 미립자 연소용 촉매 및 이를 이용하여 탄소 미립자를 연소하는 방법에 관한 것이다.
본 발명에 따른 촉매는 200 nm 이상의 다수의 대형 기공을 가지고 있어 반응물인 탄소 미립자와의 효율적으로 접촉하고, 은(Ag) 및 로듐(Rh)이 담지되어 촉매의 산화 반응 활성이 향상되고, 탄소 미립자와의 연소 반응 시 연소 온도를 낮추고, 격자 산소 생성 능력을 향상시킴으로써 탄소 미립자 물질을 효과적으로 연소시킬 수 있다.The present invention relates to a catalyst for combustion of carbon particles in which rhodium and silver are supported on a cerium oxide support having a large pore structure and a method of burning carbon particles using the same.
The catalyst according to the present invention has a large number of large pores of 200 nm or more, so that it efficiently contacts carbon particles, which are reactants, and silver (Ag) and rhodium (Rh) are supported to improve the oxidation reaction activity of the catalyst and carbon particles. By lowering the combustion temperature during the combustion reaction with and improving the lattice oxygen generation ability, carbon particulate matter can be effectively burned.
Description
본 발명은 대형 기공 구조를 갖는 세륨 산화물 지지체에 로듐 및 은을 담지한 탄소 미립자 연소용 촉매 및 이를 이용하여 탄소 미립자를 연소하는 방법에 관한 것이다.The present invention relates to a catalyst for combustion of carbon particles in which rhodium and silver are supported on a cerium oxide support having a large pore structure and a method of burning carbon particles using the same.
지구온난화가 가속화됨에 따라 CO2 규제와 더불어 자동차 배기가스에 대한 규제는 지속적으로 강화되고 있다. 강화된 배기가스 규제를 만족시키기 위해서는 차량의 연비는 향상되고 수트 (soot), 질소산화물 (NOx), 탄화수소 (HC) 등 배기 오염 물질은 감소하여야 한다. 이 중 soot은 다른 오염물질과 결합하여 탄소 고체 입자상 물질(particulate matter, PM)로 존재하며 대기 중에 존재하는 경우 인체에 심각한 영향을 주는 유해물질로 알려져 있다. As global warming accelerates, regulations on automobile exhaust gases along with CO2 regulations are continuously being strengthened. In order to meet strengthened exhaust gas regulations, vehicle fuel efficiency must be improved and exhaust pollutants such as soot, nitrogen oxides (NOx), and hydrocarbons (HC) must be reduced. Among these, soot combines with other pollutants to form carbon solid particulate matter (PM) and is known to be a hazardous substance that has serious effects on the human body when present in the air.
탄소 미립자 물질의 처리를 위해 PM 등의 탄소계 물질의 연소를 촉진시키는 촉매를 담지시킨 GPF 혹은 DPF가 이용되고 있으며, 차량의 연비 향상을 위해 저온에서도 높은 산화 성능을 보이는 촉매에 대한 연구가 지속적으로 진행되고 있다.For the treatment of carbon particulate matter, GPF or DPF carrying a catalyst that promotes combustion of carbon-based materials such as PM is used, and research is ongoing on catalysts that show high oxidation performance even at low temperatures to improve fuel efficiency of vehicles. It's going on.
PM을 제거하는 대표적인 촉매인 세륨 산화물 기반의 촉매는 산소를 효율적으로 공급할 수 있어 여러 산화 반응에서 지지체로 사용되고 있다. PM 제거 반응에서 세륨 산화물 촉매는 촉매 표면에 활성 산소를 공급하여 PM 물질 표면에서 반응하고 탄소 입자는 이산화탄소로 전환되어 제거된다.Cerium oxide-based catalysts, which are representative catalysts for removing PM, can supply oxygen efficiently and are used as supports in various oxidation reactions. In the PM removal reaction, the cerium oxide catalyst reacts on the surface of the PM material by supplying active oxygen to the catalyst surface, and the carbon particles are converted to carbon dioxide and removed.
그러나 종래 보고된 세륨 산화물 촉매의 경우 소형 기공 구조(micropore) 또는 중형 기공 구조(mesopore)를 갖고 있기 때문에 50 nm 이상의 크기를 갖는 입자가 다수 존재하고 있는 탄소 미립자 물질과의 접촉이 원활하지 않아 연소 반응 온도가 높게 형성되고, 따라서 탄소 미립자 물질을 효과적으로 연소시킬 수 없다는 문제점이 존재한다.However, since the previously reported cerium oxide catalyst has a small pore structure (micropore) or a medium sized pore structure (mesopore), it does not have smooth contact with carbon particulate matter containing many particles with a size of 50 nm or more, resulting in combustion reaction. There is a problem that the temperature is high and therefore the carbon particulate material cannot be burned effectively.
본 발명은 전술한 문제점을 해결하기 위해 안출된 것으로서, 본 발명에서는 대형 기공 구조를 갖는 세륨 산화물 지지체에 은(Ag) 및 로듐(Rh)을 담지시킴으로써 촉매와 PM 물질의 접촉 효율을 증진시키며, 격자 산소 생성 능력을 향상시켜 효과적으로 탄소 미립자 물질을 연소시키고 연소 온도를 낮출 수 있는 탄소 미립자 연소용 촉매 및 이를 이용하여 탄소 미립자를 연소하는 방법을 제공하고자 한다.The present invention was developed to solve the above-mentioned problems. In the present invention, the contact efficiency between the catalyst and the PM material is improved by supporting silver (Ag) and rhodium (Rh) on a cerium oxide support having a large pore structure, and the lattice The object of the present invention is to provide a catalyst for combustion of carbon particulates that can effectively burn particulate carbon materials and lower the combustion temperature by improving oxygen production ability, and a method of burning particulate carbon using the same.
본 발명은 상기 과제를 해결하기 위하여, In order to solve the above problems, the present invention
200 nm 이상의 다수의 대형 기공을 갖는 세륨 산화물 지지체; 상기 세륨 산화물 지지체에 담지되는 은(Ag); 및 상기 세륨 산화물 지지체에 상기 은과 혼재되어 담지되는 로듐(Rh);을 포함하는 탄소 미립자 연소용 촉매를 제공한다.Cerium oxide support with multiple large pores of 200 nm or larger; Silver (Ag) supported on the cerium oxide support; and rhodium (Rh) mixed with the silver and supported on the cerium oxide support.
본 발명에 따르면, 상기 기공은 250 nm 내지 450 nm일 수 있다.According to the present invention, the pores may be 250 nm to 450 nm.
본 발명에 따르면, 상기 로듐과 상기 은은 1:1.5 내지 1:3의 중량비로 담지될 수 있다.According to the present invention, the rhodium and the silver may be supported at a weight ratio of 1:1.5 to 1:3.
본 발명에 따르면, 상기 로듐은 1 내지 3 중량%의 함량으로 담지될 수 있다.According to the present invention, the rhodium may be supported in an amount of 1 to 3% by weight.
본 발명에 따르면, 상기 은은 3 내지 7 중량%의 함량으로 담지될 수 있다.According to the present invention, the silver may be contained in an amount of 3 to 7% by weight.
본 발명은 또한, (a) 에틸렌 글리콜과 메탄올의 혼합 용액에 세륨 전구체를 첨가 및 교반하여 용해시키는 단계; (b) 상기 세륨 전구체가 용해된 혼합 용액에 200 nm 이상의 직경을 갖는 PMMA 고분자 입자를 침전시키는 단계; 및 (c) 상기 PMMA 고분자 입자가 침전된 혼합 용액을 소성시켜, 상기 PMMA 고분자 입자를 제거하여 200 nm 이상의 다수의 대형 기공을 갖는 세륨 산화물 지지체를 제조하는 단계; (d) 상기 세륨 산화물 지지체에 은 전구체 용액을 담지 후 소성시키는 단계; 및 (e) 상기 소성된 세륨 산화물 지지체에 로듐 전구체 용액을 담지 후 소성시키는 단계;를 포함하는 탄소 미립자 연소용 촉매의 제조방법을 제공한다.The present invention also includes the steps of (a) adding and stirring a cerium precursor to a mixed solution of ethylene glycol and methanol to dissolve it; (b) precipitating PMMA polymer particles with a diameter of 200 nm or more in a mixed solution in which the cerium precursor is dissolved; and (c) calcining the mixed solution in which the PMMA polymer particles are precipitated to remove the PMMA polymer particles to prepare a cerium oxide support having a plurality of large pores of 200 nm or more; (d) placing a silver precursor solution on the cerium oxide support and then calcining it; and (e) carrying a rhodium precursor solution on the calcined cerium oxide support and calcining it.
본 발명에 따르면, 상기 탄소 미립자 연소용 촉매는 로듐과 은이 1:1.5 내지 1:3의 중량비로 담지될 수 있다.According to the present invention, the catalyst for combustion of carbon particles may contain rhodium and silver at a weight ratio of 1:1.5 to 1:3.
본 발명에 따르면, 상기 탄소 미립자 연소용 촉매는 로듐이 1 내지 3 중량%의 함량으로 담지될 수 있다.According to the present invention, the catalyst for combustion of carbon particles may contain rhodium in an amount of 1 to 3% by weight.
본 발명에 따르면, 상기 탄소 미립자 연소용 촉매는 은이 3 내지 7 중량%의 함량으로 담지될 수 있다.According to the present invention, the catalyst for combustion of carbon particles may be supported with silver in an amount of 3 to 7% by weight.
본 발명에 따르면, 상기 (d) 및 (e) 단계의 담지는 초기 젖음 담지법(incipient wetness impregnation)으로 수행될 수 있다.According to the present invention, the impregnation in steps (d) and (e) can be performed by an initial wetness impregnation method.
본 발명에 따르면, 상기 (c) 내지 (e) 단계의 소성은 400 내지 700℃에서 수행될 수 있다. According to the present invention, the calcination of steps (c) to (e) may be performed at 400 to 700°C.
본 발명은 또한, 상기 탄소 미립자 연소용 촉매를 탄소 미립자와 연소 반응시키는 단계;를 포함하는 탄소 미립자의 연소 방법을 제공한다.The present invention also provides a method for combustion of carbon particles, including the step of subjecting the catalyst for combustion of carbon particles to a combustion reaction with carbon particles.
본 발명의 특징 및 이점들은 첨부도면에 의거한 다음의 상세한 설명으로 더욱 명백해질 것이다.The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.
이에 앞서 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이고 사전적인 의미로 해석되어서는 아니되며, 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Prior to this, terms or words used in this specification and claims should not be interpreted in their usual, dictionary meaning, and the inventor may appropriately define the concept of the term in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.
본 발명에 따른 촉매는 200 nm 이상의 다수의 대형 기공을 가지고 있어 반응물인 탄소 미립자와의 효율적으로 접촉하고, 은(Ag) 및 로듐(Rh)이 담지되어 촉매의 산화 반응 활성이 향상되고, 탄소 미립자와의 연소 반응 시 연소 온도를 낮추고, 격자 산소 생성 능력을 향상시킴으로써 탄소 미립자 물질을 효과적으로 연소시킬 수 있다.The catalyst according to the present invention has a large number of large pores of 200 nm or more, so that it efficiently contacts carbon particles, which are reactants, and silver (Ag) and rhodium (Rh) are supported to improve the oxidation reaction activity of the catalyst and carbon particles. By lowering the combustion temperature during the combustion reaction with and improving the lattice oxygen generation ability, carbon particulate matter can be effectively burned.
도 1은 본 발명에 따라 제조된 Rh(2)Ag(5)Ce, PMMA, M-Rh(2)Ag(5)Ce 촉매의 SEM 이미지이다.
도 2는 본 발명에 따라 제조된 CeO2, Rh(2)Ce, Rh(2)Ag(5)Ce, M-Rh(2)Ag(5)Ce 촉매를 이용하여 탄소 미립자 모델 물질(Printex U) 연소 실험을 수행한 결과를 나타낸 그래프이다.Figure 1 is an SEM image of Rh(2)Ag(5)Ce, PMMA, and M-Rh(2)Ag(5)Ce catalyst prepared according to the present invention.
Figure 2 shows carbon particulate model material (Printex U) using CeO 2 , Rh(2)Ce, Rh(2)Ag(5)Ce, and M-Rh(2)Ag(5)Ce catalysts prepared according to the present invention. ) This is a graph showing the results of a combustion experiment.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본 발명은 탄소 미립자 연소용 촉매에 관한 것으로서, 본 발명에서는 세륨 산화물 지지체가 200 nm 이상의 대형 기공 구조를 가지도록 설계하여 촉매와 반응물의 계면 접촉을 향상시킴과 동시에, 지지체 상에 은(Ag)과 로듐(Rh)을 소정의 비율로 담지함으로써 산화 반응에 대한 촉매의 활성을 향상시켜 탄소 미립자 물질을 효과적으로 연소시킬 수 있는 탄소 미립자 연소용 촉매를 제공하고자 한다.The present invention relates to a catalyst for combustion of carbon particulates. In the present invention, the cerium oxide support is designed to have a large pore structure of 200 nm or more to improve the interfacial contact between the catalyst and the reactant, and at the same time, silver (Ag) and silver (Ag) are added on the support. An object of the present invention is to provide a catalyst for combustion of carbon particulates that can effectively burn carbon particulate materials by improving the activity of the catalyst for oxidation reactions by supporting rhodium (Rh) in a predetermined ratio.
이를 위해, 본 발명은 200 nm 이상의 다수의 대형 기공을 갖는 세륨 산화물 지지체; 상기 세륨 산화물 지지체에 담지되는 은(Ag); 및 상기 세륨 산화물 지지체에 상기 은과 혼재되어 담지되는 로듐(Rh);을 포함하는 탄소 미립자 연소용 촉매를 제공한다.To this end, the present invention provides a cerium oxide support having a large number of large pores of 200 nm or more; Silver (Ag) supported on the cerium oxide support; and rhodium (Rh) mixed with the silver and supported on the cerium oxide support.
이때, 상기 세륨 산화물 지지체의 기공은 50 nm 이상의 크기를 갖는 입자가 다량 존재하는 탄소 미립자 물질과 효율적인 접촉 공간을 제공할 수 있는 크기라면 반드시 이에 제한되는 것은 아니지만, 상기 기공의 크기는 바람직하게는 200 nm 이상일 수 있고, 더욱 바람직하게는 250 내지 450 nm일 수 있다.At this time, the pores of the cerium oxide support are not necessarily limited to a size that can provide an efficient contact space with carbon particulate material containing a large amount of particles having a size of 50 nm or more, but the pore size is preferably 200 nm. It may be more than nm, and more preferably 250 to 450 nm.
또한, 상기 은과 로듐은 상기 세륨 산화물 지지체 상에 혼재되어 담지됨으로써 산화 반응에 대한 촉매의 활성 향상을 통해 세륨 산화물 촉매의 격자 산소 생성 능력을 향상시키고, 결과적으로 탄소 미립자 물질을 효과적으로 연소시킬 수 있다. 이때, 상기 로듐과 상기 은은 1:1.5 내지 1:3의 중량비로 담지되는 것이 바람직하고다.In addition, the silver and rhodium are mixed and supported on the cerium oxide support to improve the lattice oxygen generation ability of the cerium oxide catalyst by improving the activity of the catalyst for the oxidation reaction, and as a result, carbon particulate matter can be effectively burned. . At this time, it is preferable that the rhodium and silver are supported at a weight ratio of 1:1.5 to 1:3.
또한, 하기 실시예의 결과로부터 알 수 있는 바와 같이, 상기 로듐은 상기 세륨 산화물 지지체를 전체 중량을 기준으로 1 내지 3 중량%의 함량으로 담지되는 것이 바람직하며, 2 중량%의 함량으로 담지되는 것이 가장 바람직하다. 상기 함량 범위로 로듐이 담지될 경우 산화 반응에 대한 촉매의 활성 향상을 통해 세륨 산화물 촉매의 격자 산소 생성 능력을 향상시키고, 결과적으로 탄소 미립자 물질을 효과적으로 연소시킬 수 있다.In addition, as can be seen from the results of the following examples, the rhodium is preferably supported in an amount of 1 to 3% by weight based on the total weight of the cerium oxide support, and is most preferably supported in an amount of 2% by weight. desirable. When rhodium is supported in the above content range, the lattice oxygen generation ability of the cerium oxide catalyst is improved by improving the catalyst's activity for oxidation reaction, and as a result, carbon particulate material can be effectively burned.
또한, 하기 실시예의 결과로부터 알 수 있는 바와 같이, 상기 은은 상기 세륨 산화물 지지체를 전체 중량을 기준으로 3 내지 7 중량%의 함량으로 담지되는 것이 바람직하며, 5 중량%의 함량으로 담지되는 것이 가장 바람직하다. 상기 함량 범위로 은이 담지될 경우 산화 반응에 대한 촉매의 활성 향상을 통해 세륨 산화물 촉매의 격자 산소 생성 능력을 향상시키고, 결과적으로 탄소 미립자 물질을 효과적으로 연소시킬 수 있다.In addition, as can be seen from the results of the following examples, the silver is preferably supported in an amount of 3 to 7% by weight based on the total weight of the cerium oxide support, and most preferably in an amount of 5% by weight. do. When silver is supported in the above content range, the lattice oxygen generation ability of the cerium oxide catalyst is improved by improving the catalyst's activity for oxidation reaction, and as a result, carbon particulate material can be effectively burned.
본 발명은 또한, (a) 에틸렌 글리콜과 메탄올의 혼합 용액에 세륨 전구체를 첨가 및 교반하여 용해시키는 단계; (b) 상기 세륨 전구체가 용해된 혼합 용액에 200 nm 이상의 직경을 갖는 PMMA 고분자 입자를 침전시키는 단계; 및 (c) 상기 PMMA 고분자 입자가 침전된 혼합 용액을 소성시켜, 상기 PMMA 고분자 입자를 제거하여 200 nm 이상의 다수의 대형 기공을 갖는 세륨 산화물 지지체를 제조하는 단계; (d) 상기 세륨 산화물 지지체에 은 전구체 용액을 담지 후 소성시키는 단계; 및 (e) 상기 소성된 세륨 산화물 지지체에 로듐 전구체 용액을 담지 후 소성시키는 단계;를 포함하는 탄소 미립자 연소용 촉매의 제조방법을 제공한다.The present invention also includes the steps of (a) adding and stirring a cerium precursor to a mixed solution of ethylene glycol and methanol to dissolve it; (b) precipitating PMMA polymer particles with a diameter of 200 nm or more in a mixed solution in which the cerium precursor is dissolved; and (c) calcining the mixed solution in which the PMMA polymer particles are precipitated to remove the PMMA polymer particles to prepare a cerium oxide support having a plurality of large pores of 200 nm or more; (d) placing a silver precursor solution on the cerium oxide support and then calcining it; and (e) carrying a rhodium precursor solution on the calcined cerium oxide support and calcining it.
이때, 전술한 바와 같이, 상기 탄소 미립자 연소용 촉매는 로듐과 은이 1:1.5 내지 1:3의 중량비로 담지되는 것이 바람직하다.At this time, as described above, the catalyst for combustion of carbon particles preferably contains rhodium and silver at a weight ratio of 1:1.5 to 1:3.
또한, 전술한 바와 같이, 상기 탄소 미립자 연소용 촉매는 로듐이 1 내지 3 중량%의 함량으로 담지되는 것이 바람직하고, 은이 3 내지 7 중량%의 함량으로 담지되는 것이 바람직하다.In addition, as described above, the catalyst for combustion of carbon particulates preferably contains rhodium in an amount of 1 to 3% by weight, and silver in an amount of 3 to 7% by weight.
또한, 상기 세륨 전구체는 세슘을 제공할 수 있는 염이라면 특별히 한정되지 않으며, 예를 들어 세륨(III)아세테이트하이드레이트(cerium(III) acetate hydrate), 세륨(III)아세틸아세토네이트하이드레이트(cerium(III) acetylacetonate hydrate), 세륨(III)브로마이드(cerium(III) bromide), 세륨(III)카보네이트하이드레이트(cerium(III) carbonate hydrate), 세륨(III)클로라이드(cerium(III) chloride), 세륨(III)클로라이드헵타하이드레이트(cerium(III) chloride heptahydrate), 세륨(III)2-에틸헥사노에이트(cerium(III) 2-ethylhexanoate), 세륨(III)플로라이드(cerium(III) fluoride), 세륨(IV)플로라이드(cerium(IV) fluoride), 세륨(IV)하이드록사이드(cerium(IV) hydroxide), 세륨(III)아이오다이드(cerium(III) iodide), 세륨(III)나이트레이트헥사하이드레이트(cerium(III) nitrate hexahydrate), 세륨(III)옥살레이트하이드레이트(cerium(III) oxalate hydrate), 세륨(III)설페이트(cerium(III) sulfate), 세륨(III)설페이트하이드레이트(cerium(III) sulfate hydrate) 및 세륨(IV)설페이트(cerium(IV) sulfate) 로 이루어진 군에서 선택될 수 있다.In addition, the cerium precursor is not particularly limited as long as it is a salt that can provide cesium, for example, cerium(III) acetate hydrate, cerium(III) acetylacetonate hydrate (cerium(III) acetylacetonate hydrate, cerium(III) bromide, cerium(III) carbonate hydrate, cerium(III) chloride, cerium(III) chloride Heptahydrate (cerium(III) chloride heptahydrate), cerium(III) 2-ethylhexanoate, cerium(III) fluoride, cerium(IV) fluoride Cerium(IV) fluoride, cerium(IV) hydroxide, cerium(III) iodide, cerium(III) nitrate hexahydrate III) nitrate hexahydrate, cerium (III) oxalate hydrate, cerium (III) sulfate, cerium (III) sulfate hydrate and It may be selected from the group consisting of cerium(IV) sulfate.
또한, 상기 은 전구체는 은을 제공할 수 있는 염이라면 특별히 한정되지 않으며, 예를 들어 실버 클로라이드(AgCl), 실버 브로마이드(AgBr), 실버 이오다이드(AgI), 실버 아세테이트(Ag(OAc)), 실버 설페이트(Ag2SO4), 실버 나이트레이트(AgNO3) 및 실버 카보네이트(Ag2CO3)로 이루어진 군에서 선택될 수 있다.In addition, the silver precursor is not particularly limited as long as it is a salt that can provide silver, for example, silver chloride (AgCl), silver bromide (AgBr), silver iodide (AgI), silver acetate (Ag(OAc)) , silver sulfate (Ag 2 SO 4 ), silver nitrate (AgNO 3 ), and silver carbonate (Ag 2 CO 3 ).
또한, 상기 로듐 전구체는 로듐을 제공할 수 있는 염이라면 특별히 한정되지 않으며, 예를 들어 로듐(III)나이트레이트하이드레이트(rhodium(III) nitrate hydrate) 또는 로듐(III)클로라이드하이드레이트(Rhodium(Ⅲ) chloride hydrate)일 수 있다.In addition, the rhodium precursor is not particularly limited as long as it is a salt that can provide rhodium, for example, rhodium (III) nitrate hydrate or rhodium (III) chloride. hydrate).
또한, 상기 (d) 및 (e) 단계의 담지는 초기 젖음 담지법(incipient wetness impregnation method)으로 수행될 수 있다. 초기 젖음 담지법에 따른 담지의 경우, 은 전구체 용액과 로듐 전구체 용액이 충분히 담지되도록 수차례 담지 공정을 반복하고, 담지마다 건조 과정을 거칠 수 있다.Additionally, the impregnation in steps (d) and (e) may be performed using an incipient wetness impregnation method. In the case of support according to the initial wet support method, the support process may be repeated several times to ensure that the silver precursor solution and the rhodium precursor solution are sufficiently supported, and a drying process may be performed for each support.
또한, 상기 (c) 내지 (e) 단계의 소성은 400 내지 700℃에서 수행되는 것이 바람직하다.Additionally, the calcination in steps (c) to (e) is preferably performed at 400 to 700°C.
또한, 본 발명은 상기 탄소 미립자 연소용 촉매를 탄소 미립자와 연소 반응시키는 단계;를 포함하는 탄소 미립자의 연소 방법을 제공한다.In addition, the present invention provides a method for combustion of carbon particles, including the step of subjecting the catalyst for combustion of carbon particles to a combustion reaction with carbon particles.
[실시예][Example]
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
실시예Example . 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 . Silver and rhodium are deposited on a cerium oxide support with a large pore structure. 담지된supported 촉매(M-Rh(2)Ag(5)Ce)의 제조 Preparation of catalyst (M-Rh(2)Ag(5)Ce)
(1) 대형 기공 구조를 갖는 세륨 산화물 지지체(M-(1) Cerium oxide support with large pore structure (M- CeOCeO 22 )의 제조)Manufacture of
대형 기공 구조를 갖는 CeO2 지지체를 제조하기 위하여, 먼저 PMMA 고분자 입자를 합성하였다. 이를 위해 증류수 560 ml에 메틸 메타아크릴에이트(methyl methacrylate, MMA, Sigma Aldrich) 240 ml와 포타슘 펄서페이트 (potassium persulfate, Sigma Aldrich) 1.62 g을 혼합하고, 아르고 가스 분위기에서 70℃에서 2 시간 교반한 후, 15000 rpm에서 20 분간 원심분리하여 약 350 nm의 크기를 갖는 PMMA (poly methyl methacrylate) 입자를 분리하였다. 분리된 PMMA 입자는 60℃에서 12 시간 동안 건조 후 보관하였다.To prepare a CeO 2 support with a large pore structure, PMMA polymer particles were first synthesized. For this purpose, 240 ml of methyl methacrylate (MMA, Sigma Aldrich) and 1.62 g of potassium persulfate (Sigma Aldrich) were mixed with 560 ml of distilled water, and stirred for 2 hours at 70°C in an argo gas atmosphere. , PMMA (poly methyl methacrylate) particles with a size of approximately 350 nm were separated by centrifugation at 15,000 rpm for 20 minutes. The separated PMMA particles were dried at 60°C for 12 hours and then stored.
다음으로, 에틸렌 글리콜(ethylene glycol, Sigma Aldrich) 15ml와 메탄올(methanol, Sigma Aldrich) 10 ml 혼합 용액에 세륨 나이트레이트 헥사하이드레이트(Cerium (Cerium(III) nitrate hexahydrate, Sigma Aldrich) 21.7 g을 교반하여 용해시키고, 상기 합성한 PMMA 10 g을 4 시간 동안 침전시키고, 진공 연결된 깔때기를 이용하여 용액을 여과시켜 상기 혼합 용액을 PMMA 입자에 침투시켰다. 다음으로, 상기 혼합 용액이 침투된 PMMA 입자를 공기 200 ml/min 분위기에서 1℃/min으로 승온하며 550℃에서 5 시간 동안 소성시켜 PMMA 고분자를 연소 및 제거함으로써 250 nm 이상의 대형 기공을 가지는 가루형태의 세륨 산화물 지지체(M-CeO2)를 제조하였다.Next, 21.7 g of Cerium (Cerium(III) nitrate hexahydrate, Sigma Aldrich) was stirred and dissolved in a mixed solution of 15 ml of ethylene glycol (Sigma Aldrich) and 10 ml of methanol (Sigma Aldrich). 10 g of the synthesized PMMA was precipitated for 4 hours, and the solution was filtered using a vacuum-connected funnel to infiltrate the PMMA particles. Next, the PMMA particles infiltrated with the mixed solution were placed in 200 ml of air. Powdered cerium oxide support (M-CeO 2 ) with large pores of 250 nm or more was prepared by burning and removing the PMMA polymer by firing at 550°C for 5 hours while raising the temperature at 1°C/min in an atmosphere /min.
(2) 대형 기공 구조를 갖는 세륨 산화물 지지체에 은((2) Silver ( AgAg )을 )second 담지한supported 촉매(M-Ag(5)Ce)의 제조 Preparation of catalyst (M-Ag(5)Ce)
상기 세륨 산화물 지지체(M-CeO2)의 중량 대비 5 중량%의 은이 담지되도록 은 전구체(silver nitrate, Sigma Aldrich) 용액을 초기젖음법(Incipient wetness method)으로 첨가하고 110℃에서 12시간 건조하였다. 이후, 5℃/min으로 승온하며 550℃에서 소성하여 가루형태의 은 담지 세륨 산화물 촉매 M-Ag(5)Ce를 제조하였다.A silver precursor (silver nitrate, Sigma Aldrich) solution was added using the initial wetness method to support 5% by weight of silver based on the weight of the cerium oxide support (M-CeO 2 ) and dried at 110°C for 12 hours. Afterwards, the temperature was raised at 5°C/min and fired at 550°C to prepare silver-supported cerium oxide catalyst M-Ag(5)Ce in powder form.
(3) 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 (3) Silver and rhodium were deposited on a cerium oxide support with a large pore structure. 담지된supported 촉매(M-Rh(2)Ag(5)Ce)의 제조 Preparation of catalyst (M-Rh(2)Ag(5)Ce)
2 중량%의 로듐이 상기 은이 담지된 CeO2 촉매(M-Ag(5)Ce)에 담지되도록 로듐 전구체(rhodium nitrate hydrate, Sigma Aldrich) 용액을 초기젖음법(Incipient wetness method)으로 첨가하고 110℃에서 12시간 건조하였다. 이후, 5℃/min으로 승온하며 550℃에서 소성하여 가루형태의 로듐, 은 담지 세륨 산화물 촉매 M-Rh(2)Ag(5)Ce를 제조하였다.A rhodium precursor (rhodium nitrate hydrate, Sigma Aldrich) solution was added using the initial wetness method so that 2% by weight of rhodium was supported on the silver-supported CeO 2 catalyst (M-Ag(5)Ce) and incubated at 110°C. It was dried for 12 hours. Thereafter, the temperature was raised at 5°C/min and fired at 550°C to prepare rhodium and silver-supported cerium oxide catalyst M-Rh(2)Ag(5)Ce in powder form.
비교예Comparative example 1. 중형 기공 구조를 갖는 1. Having a medium-sized pore structure CeOCeO 22 지지체에 로듐(Rh)을 Rhodium (Rh) is added to the support. 담지한supported 촉매 제조 catalyst manufacturing
먼저, 세륨 나이트레이트 헥사하이드레이트(Cerium(III) nitrate hexahydrate, Sigma Aldrich)를 5℃/min으로 승온하며 550℃에서 4시간 동안 소성시켜 중형 기공 구조를 갖는 세륨 산화물 지지체를 제조하였다. First, cerium(III) nitrate hexahydrate (Sigma Aldrich) was heated at 5°C/min and calcined at 550°C for 4 hours to prepare a cerium oxide support having a medium-sized pore structure.
다음으로, 2 중량%의 로듐이 상기 중형 기공 구조를 갖는 CeO2 지지체에 담지되도록 로듐 전구체(rhodium nitrate hydrate, Sigma Aldrich) 용액을 초기젖음법(Incipient wetness method)으로 첨가하고 110℃에서 12시간 건조하였다. 이후, 5℃/min으로 승온하며 550℃에서 소성하여 가루형태의 로듐 담지 세륨 산화물 촉매 Rh(2)Ce를 제조하였다.Next, a rhodium precursor (rhodium nitrate hydrate, Sigma Aldrich) solution was added using the initial wetness method so that 2% by weight of rhodium was supported on the CeO 2 support having the medium pore structure, and dried at 110°C for 12 hours. did. Thereafter, the temperature was raised at 5°C/min and fired at 550°C to prepare rhodium-supported cerium oxide catalyst Rh(2)Ce in powder form.
비교예Comparative example 2. 중형 기공 구조를 갖는 2. Having a meso-sized pore structure CeOCeO 22 지지체에 은( Silver on the support ( AgAg )을 )second 담지한supported 촉매 제조 catalyst manufacturing
상기 비교예 1에서 제조한 중형 기공 구조를 갖는 세륨 산화물 지지체에 5 중량%의 은이 담지되도록 은 전구체 (silver nitrate, Sigma Aldrich) 용액을 초기젖음법(Incipient wetness method)으로 첨가하고 110℃에서 12시간 건조하였다. 이후, 5℃/min으로 승온하며 550℃에서 소성하여 가루형태의 은 담지 세륨 산화물 촉매 Ag(5)Ce를 제조하였다.A silver precursor (silver nitrate, Sigma Aldrich) solution was added by the initial wetness method so that 5% by weight of silver was supported on the cerium oxide support having a medium-sized pore structure prepared in Comparative Example 1, and incubated at 110° C. for 12 hours. It was dried. Afterwards, the temperature was raised at 5°C/min and fired at 550°C to prepare silver-supported cerium oxide catalyst Ag(5)Ce in powder form.
비교예Comparative example 3. 중형 기공 구조를 갖는 3. Having a meso-sized pore structure CeOCeO 22 지지체에 은( Silver on the support ( AgAg ), 로듐(Rh)을 ), rhodium (Rh) 담지한supported 촉매 제조 catalyst manufacturing
2 중량%의 로듐이 상기 비교예 2의 은이 담지된 CeO2 촉매(Ag(5)Ce)에 담지되도록 로듐 전구체(rhodium nitrate hydrate, Sigma Aldrich) 용액을 초기젖음법(Incipient wetness method)으로 첨가하고 110℃에서 12시간 건조하였다. 이후, 5℃/min으로 승온하며 550℃에서 소성하여 가루형태의 로듐, 은 담지 세륨 산화물 촉매 Rh(2)Ag(5)Ce를 제조하였다.A rhodium precursor (rhodium nitrate hydrate, Sigma Aldrich) solution was added using the initial wetness method so that 2% by weight of rhodium was supported on the silver-supported CeO 2 catalyst (Ag(5)Ce) of Comparative Example 2. It was dried at 110°C for 12 hours. Afterwards, the temperature was raised at 5°C/min and fired at 550°C to prepare rhodium and silver-supported cerium oxide catalyst Rh(2)Ag(5)Ce in powder form.
실험예Experiment example 1. One. SEMS.E.M. 이미지 분석 image analysis
도 1의 (a)는 비교예 3에 따른 중형 기공 구조를 갖는 CeO2 지지체에 은(Ag), 로듐(Rh)이 담지된 촉매 Rh(2)Ag(5)Ce의 SEM 이미지이고, (b)는 대형 기공을 갖는 CeO2 지지체의 제조에 사용된 PMMA 고분자의 SEM 이미지이며, (c), (d)는 본 발명의 실시예에 따른 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 담지된 촉매 M-Rh(2)Ag(5)Ce)의 저배율(c) 및 고배율(d) SEM 이미지이다.Figure 1 (a) is an SEM image of the catalyst Rh(2)Ag(5)Ce in which silver (Ag) and rhodium (Rh) were supported on a CeO 2 support with a medium-sized pore structure according to Comparative Example 3, (b) ) is an SEM image of the PMMA polymer used in the production of a CeO 2 support with large pores, and (c) and (d) are SEM images of silver and rhodium supported on a cerium oxide support with a large pore structure according to an embodiment of the present invention. These are low-magnification (c) and high-magnification (d) SEM images of the catalyst M-Rh(2)Ag(5)Ce).
도 1을 통해, 약 10 nm 크기의 중형 기공 구조를 갖는 CeO2 지지체를 이용한 비교예 3의 촉매 Rh(2)Ag(5)Ce는 대형 기공 구조가 전혀 관찰되지 않는 반면, 약 350 nm 크기를 갖는 PMMA 입자를 이용하여 제조된 본 발명의 실시예에 따른 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 담지된 촉매 M-Rh(2)Ag(5)Ce)는 250 내지 450 nm의 대형 기공 구조를 갖는다는 것을 확인하였다. 1, the catalyst Rh(2)Ag(5)Ce of Comparative Example 3 using a CeO 2 support with a medium-sized pore structure of about 10 nm does not have a large pore structure at all, whereas the catalyst has a pore size of about 350 nm. Catalyst M-Rh(2)Ag(5)Ce), in which silver and rhodium are supported on a cerium oxide support with a large pore structure according to an embodiment of the present invention manufactured using PMMA particles, has a large pore size of 250 to 450 nm. It was confirmed that it had a pore structure.
실험예Experiment example 2. 2. PrintexPrintex U 연소 실험 U Combustion Experiment
상기 실시예 및 비교예에 따라 제조된 촉매들에 대하여 자동차 배기가스에 포함된 탄소 미립자 모델 물질로 Printex U를 사용하여 연소 실험을 수행하였다.Combustion experiments were performed on the catalysts prepared according to the above examples and comparative examples using Printex U as a model material for carbon particles contained in automobile exhaust gas.
구체적으로, 막대 사발을 이용하여 상기 촉매들 20 mg을 각각 2 mg의 Printex U와 혼합한 후 석영 관에 넣고, 20 ml/min O2, 80 ml/min He, 5 vol.% 수증기가 포함된 조건에서 700℃까지 5℃/min로 승온하며 온도에 따른 Printex U 연소 반응을 진행하였다. 이때, 승온 반응 중 생성되는 CO2의 농도가 가장 높은 온도를 Tm으로 설정하였다.Specifically, 20 mg of the above catalysts were mixed with 2 mg of Printex U each using a bar bowl and then placed in a quartz tube, containing 20 ml/min O 2 , 80 ml/min He, and 5 vol.% water vapor. Under these conditions, the temperature was raised to 700°C at 5°C/min, and the Printex U combustion reaction was performed depending on the temperature. At this time, the temperature at which the concentration of CO 2 produced during the temperature increase reaction was highest was set as T m .
도 2는 본 발명에 따라 제조된 CeO2, Rh(2)Ce, Rh(2)Ag(5)Ce, M-Rh(2)Ag(5)Ce 촉매를 이용하여 탄소 미립자 모델 물질(Printex U) 연소 실험을 수행한 결과를 나타낸 그래프이다.Figure 2 shows carbon particulate model material (Printex U) using CeO 2 , Rh(2)Ce, Rh(2)Ag(5)Ce, and M-Rh(2)Ag(5)Ce catalysts prepared according to the present invention. ) This is a graph showing the results of a combustion experiment.
도 2의 결과를 통해, 세륨 산화물 지지체에 로듐, 또는 로듐과 은이 혼재되어 담지될 경우 높은 환원성 및 저온에서의 활성 산소종 활용에 따른 촉매의 활성 및 연소 효율이 현저하게 상승하는 것을 확인할 수 있었다. 또한, 동일하게 로듐과 은이 담지되더라도, 중형 기공 구조를 갖는 CeO2 지지체를 이용한 비교예 3의 촉매 Rh(2)Ag(5)Ce 대비 본 발명에 따른 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 담지된 촉매 M-Rh(2)Ag(5)Ce (T20 = 369℃, T50 = 451℃)의 활성이 촉매와 PM의 접촉 효율 증가에 따라 현저하게 향상됨을 확인하였다.Through the results in Figure 2, it was confirmed that when rhodium or a mixture of rhodium and silver is supported on a cerium oxide support, the activity and combustion efficiency of the catalyst due to high reducibility and utilization of reactive oxygen species at low temperatures are significantly increased. In addition, even if rhodium and silver were supported equally, silver and silver were added to the cerium oxide support having a large pore structure according to the present invention compared to the Rh( 2 )Ag(5)Ce catalyst of Comparative Example 3 using a CeO 2 support having a medium pore structure. It was confirmed that the activity of the rhodium-supported catalyst M-Rh(2)Ag(5)Ce (T 20 = 369°C, T 50 = 451°C) was significantly improved as the contact efficiency between the catalyst and PM increased.
실험예Experiment example 3. H 3.H 22 -- TPRTPR 및 soot- and soot- TPRTPR 분석 analyze
다음으로, H2-TPR과 soot-TPR 분석을 이용하여 상기 실시예 및 비교예에 따라 제조된 촉매들의 contact 효율을 비교하였다. Next, the contact efficiencies of catalysts prepared according to the above Examples and Comparative Examples were compared using H 2 -TPR and soot-TPR analysis.
하기 표 1은 중형 기공 구조를 갖는 CeO2 지지체를 이용한 비교예 3의 촉매 Rh(2)Ag(5)Ce와 본 발명에 따른 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 담지된 촉매 M-Rh(2)Ag(5)Ce의 H2-TPR, soot-TPR의 산소 소모량 및 이들 비율로 도출한 접촉 효율(contact efficiency)를 나타낸 것이다.Table 1 below shows Catalyst Rh(2)Ag(5)Ce of Comparative Example 3 using a CeO 2 support with a medium-sized pore structure and Catalyst M in which silver and rhodium were supported on a cerium oxide support with a large pore structure according to the present invention. This shows the oxygen consumption of H 2 -TPR and soot-TPR of -Rh(2)Ag(5)Ce and the contact efficiency derived from these ratios.
상기 표 1에 나타난 결과를 통해, 중형 기공 구조를 갖는 CeO2 지지체를 이용한 비교예 3의 촉매 Rh(2)Ag(5)Ce는 산소 공급 능력은 우수하나, 접촉 효율이 낮아 결과적으로 PM에 산소를 공급하는 능력이 현저하게 낮은 반면, 본 발명에 따른 대형 기공 구조를 갖는 세륨 산화물 지지체에 은과 로듐이 담지된 촉매 M-Rh(2)Ag(5)Ce는 상대적으로 낮은 산소 공급능력을 나타내지만, PM에서의 기체 접촉량이 크게 증가함에 따라 접촉 효율이 약 7배 이상 증가하여 PM에 산소를 공급하는 능력이 현저하게 향상되어, 결과적으로 탄소 미립자 물질을 효과적으로 연소시킬 수 있음을 확인하였다.Through the results shown in Table 1, the Rh(2)Ag(5)Ce catalyst of Comparative Example 3 using a CeO 2 support with a medium-sized pore structure has excellent oxygen supply ability, but has low contact efficiency, resulting in oxygen in PM. While the ability to supply is significantly low, the catalyst M-Rh(2)Ag(5)Ce, in which silver and rhodium are supported on a cerium oxide support with a large pore structure according to the present invention, shows a relatively low oxygen supply ability. However, as the amount of gas contact in the PM greatly increased, the contact efficiency increased by about 7 times or more, significantly improving the ability to supply oxygen to the PM, and as a result, it was confirmed that carbon particulate matter could be effectively burned.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시형태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
상기 세륨 산화물 지지체에 담지되는 은(Ag); 및
상기 세륨 산화물 지지체에 상기 은과 혼재되어 담지되는 로듐(Rh);을 포함하는 탄소 미립자 연소용 촉매.Cerium oxide support with multiple large pores of 200 nm or larger;
Silver (Ag) supported on the cerium oxide support; and
A catalyst for combustion of carbon particles comprising rhodium (Rh) mixed with the silver and supported on the cerium oxide support.
상기 기공은 250 nm 내지 450 nm인 것을 특징으로 하는 탄소 미립자 연소용 촉매.According to paragraph 1,
A catalyst for combustion of carbon particulates, characterized in that the pores are 250 nm to 450 nm.
상기 로듐과 상기 은은 1:1.5 내지 1:3의 중량비로 담지되는 것을 특징으로 하는 탄소 미립자 연소용 촉매.According to paragraph 1,
A catalyst for combustion of carbon particulates, characterized in that the rhodium and the silver are supported at a weight ratio of 1:1.5 to 1:3.
상기 로듐은 1 내지 3 중량%의 함량으로 담지되는 것을 특징으로 하는 탄소 미립자 연소용 촉매.According to paragraph 1,
A catalyst for combustion of carbon particulates, characterized in that the rhodium is supported in an amount of 1 to 3% by weight.
상기 은은 3 내지 7 중량%의 함량으로 담지되는 것을 특징으로 하는 탄소 미립자 연소용 촉매.According to paragraph 1,
A catalyst for combustion of carbon particulates, characterized in that the silver is supported in an amount of 3 to 7% by weight.
(b) 상기 세륨 전구체가 용해된 혼합 용액에 200 nm 이상의 직경을 갖는 PMMA 고분자 입자를 침전시키는 단계; 및
(c) 상기 PMMA 고분자 입자가 침전된 혼합 용액을 소성시켜, 상기 PMMA 고분자 입자를 제거하여 200 nm 이상의 다수의 대형 기공을 갖는 세륨 산화물 지지체를 제조하는 단계;
(d) 상기 세륨 산화물 지지체에 은 전구체 용액을 담지 후 소성시키는 단계; 및
(e) 상기 소성된 세륨 산화물 지지체에 로듐 전구체 용액을 담지 후 소성시키는 단계;를 포함하는 탄소 미립자 연소용 촉매의 제조방법.(a) adding and stirring a cerium precursor to a mixed solution of ethylene glycol and methanol to dissolve it;
(b) precipitating PMMA polymer particles with a diameter of 200 nm or more in a mixed solution in which the cerium precursor is dissolved; and
(c) calcining the mixed solution in which the PMMA polymer particles are precipitated to remove the PMMA polymer particles to prepare a cerium oxide support having a plurality of large pores of 200 nm or more;
(d) placing a silver precursor solution on the cerium oxide support and then calcining it; and
(e) carrying a rhodium precursor solution on the calcined cerium oxide support and calcining it.
상기 탄소 미립자 연소용 촉매는 로듐과 은이 1:1.5 내지 1:3의 중량비로 담지된 것을 특징으로 하는 탄소 미립자 연소용 촉매의 제조방법.According to clause 6,
A method of producing a catalyst for combustion of carbon particles, characterized in that the catalyst for combustion of carbon particles is supported by rhodium and silver at a weight ratio of 1:1.5 to 1:3.
상기 탄소 미립자 연소용 촉매는 로듐이 1 내지 3 중량%의 함량으로 담지된 것을 특징으로 하는 탄소 미립자 연소용 촉매의 제조방법.According to clause 6,
A method for producing a catalyst for combustion of carbon particles, characterized in that the catalyst for combustion of carbon particles is supported with rhodium in an amount of 1 to 3% by weight.
상기 탄소 미립자 연소용 촉매는 은이 3 내지 7 중량%의 함량으로 담지된 것을 특징으로 하는 탄소 미립자 연소용 촉매의 제조방법.According to clause 6,
A method of producing a catalyst for combustion of carbon particles, characterized in that the catalyst for combustion of carbon particles is supported with silver in an amount of 3 to 7% by weight.
상기 (d) 및 (e) 단계의 담지는 초기 젖음 담지법(incipient wetness impregnation)으로 수행되는 것을 특징으로 하는 탄소 미립자 연소용 촉매의 제조방법.According to clause 6,
A method for producing a catalyst for combustion of carbon particulates, characterized in that the supporting in steps (d) and (e) is carried out by an initial wetness impregnation.
상기 (c) 내지 (e) 단계의 소성은 400 내지 700℃에서 수행되는 것을 특징으로 하는 탄소 미립자 연소용 촉매의 제조방법.According to clause 6,
A method for producing a catalyst for combustion of carbon particulates, characterized in that the calcination in steps (c) to (e) is performed at 400 to 700 ° C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020220083865 | 2022-07-07 | ||
| KR20220083865 | 2022-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20240007879A true KR20240007879A (en) | 2024-01-17 |
Family
ID=89713440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020230086787A KR20240007879A (en) | 2022-07-07 | 2023-07-04 | Catalyst for combustion of carbon particulate matter using rhodium and silver impregnated on macroporous ceria support, and method for carbon particulate matter combustion using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20240007879A (en) |
-
2023
- 2023-07-04 KR KR1020230086787A patent/KR20240007879A/en unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR920009112B1 (en) | Three-way catalysts for lean exhaust system | |
| JP3741303B2 (en) | Exhaust gas purification catalyst | |
| US7759278B2 (en) | Exhaust gas-purifying catalyst | |
| KR20150122219A (en) | Oxidation catalyst for internal combustion engine exhaust gas treatment | |
| WO1997037761A1 (en) | Exhaust gas purifying catalyst and exhaust gas purifying method | |
| JP2005262201A (en) | Exhaust gas-cleaning catalyst and method for manufacturing the same | |
| EP1913999A1 (en) | Exhaust gas purifying catalyst | |
| CN111604050A (en) | Preparation and application of spongy natural gas engine tail gas catalyst | |
| CN107262089B (en) | Exhaust gas purifying catalyst | |
| CN113385188B (en) | Integral cDPF composite material for diesel vehicle and preparation method thereof | |
| JP2006314894A (en) | Production method of catalyst for cleaning emission gas | |
| CN100337726C (en) | Catalyst for purifying exhaust gases and process for producing the same | |
| CN111379613B (en) | Diesel particulate trap loaded with macroporous perovskite oxide and application thereof | |
| KR20240007879A (en) | Catalyst for combustion of carbon particulate matter using rhodium and silver impregnated on macroporous ceria support, and method for carbon particulate matter combustion using the same | |
| JP2013180283A (en) | Oxidation catalyst and exhaust gas cleaning method using the same | |
| JP2006043683A (en) | Catalyst carrier and its manufacturing method and catalyst for cleaning exhaust gas | |
| KR102332047B1 (en) | Low-temperature de-NOx catalyst using ceria-alumina complex support and manufacturing method thereof | |
| JPH0582258B2 (en) | ||
| JP4330666B2 (en) | Exhaust gas purification catalyst and exhaust gas purification method | |
| CN114713217A (en) | Modified cerium oxide carrier and modification method thereof, palladium-cerium catalyst and preparation method and application thereof | |
| CN1210104C (en) | Sundex low-temperature catalytic combustion nanometre composite oxide catalyst and preparing method thereof | |
| JPH08323205A (en) | Exhaust gas purifying catalyst and its production | |
| JP2003326137A (en) | Exhaust gas purification method and catalyst for exhaust gas purification | |
| JP2006341152A (en) | Catalyst carrier manufacturing method and manufacturing method of exhaust gas purifying catalyst | |
| JP2005052805A (en) | Exhaust gas cleaning catalyst and manufacturing method therefor |