KR100249732B1 - Preparation of metallic honeycomb for removing nox of diesel automotives - Google Patents
Preparation of metallic honeycomb for removing nox of diesel automotives Download PDFInfo
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- KR100249732B1 KR100249732B1 KR1019970015145A KR19970015145A KR100249732B1 KR 100249732 B1 KR100249732 B1 KR 100249732B1 KR 1019970015145 A KR1019970015145 A KR 1019970015145A KR 19970015145 A KR19970015145 A KR 19970015145A KR 100249732 B1 KR100249732 B1 KR 100249732B1
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- Prior art keywords
- diesel
- metal honeycomb
- exhaust gas
- honeycomb
- nox
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 241000264877 Hippospongia communis Species 0.000 claims description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 239000004071 soot Substances 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 229910002089 NOx Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 230000003137 locomotive effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
본 발명은 경유 및 디젤 연료를 사용하는 원동기관 예컨데 자동차의 배기 가스에 포함되는 NOx, SOx, CO, 미반응 탄화수소(HC), 매연분진 등을 효과적으로 제거하는 경유 및 디젤 자동차용 배기가스 정화용 촉매를 담지한 금속 하니컴 및 그 제작방법에 관한 것으로, 구조는 간단하면서 정화능률이 뛰어나고 자동차(원동기관)의 배기유로나 기존의 자동차 머플러에 쉽게 장착할 수 있을 뿐만 아니라 자동차 배터리로 예열하여 시동초기에도 배기가스의 오염물질을 효과적으로 분해 및 제거할 수 있도록 한 것이다.The present invention provides a catalyst for purifying exhaust gas for diesel and diesel vehicles, which effectively removes NOx, SOx, CO, unreacted hydrocarbons (HC), soot dust, etc. contained in exhaust gas of automobiles. The present invention relates to a supported metal honeycomb and its manufacturing method. The structure is simple and excellent in purifying efficiency, and can be easily installed in the exhaust path of an automobile (drive engine) or an existing automobile muffler, and is also preheated with a car battery and exhausted at the start-up It is designed to effectively decompose and remove gaseous pollutants.
Description
도 1 : 본 발명의 외관 사시도.1 is an external perspective view of the present invention.
도 2 : 본 발명 일실시예의 단면구성도.2 is a cross-sectional view of an embodiment of the present invention.
도 3 : 본 발명 하니컴의 일부분 사시도.3 is a partial perspective view of the honeycomb of the present invention.
도 4 : 본 발명 제 3 도의 다른 실시예 사시도.4 is a perspective view of another embodiment of the third embodiment of the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
(가) : 금속 하니컴 (1) : 배기가스 배출통로(A): Metal honeycomb (1): Exhaust gas exhaust passage
(2) : 관체 (4)(6)(8) : 금속 하니컴(2): tube (4) (6) (8): metal honeycomb
(10) : 접지선 (12)(14) : 전원 공급선10:
본 발명은 경유 및 디젤 연료를 사용하는 원동기관 예컨데 자동차의 배기 가스에 포함되는 NOx, SOx, CO, 미반응 탄화수소(HC), 매연분진 등을 효과적으로 제거한는 경유 및 디젤 자동차용 배기가스 정화용 촉매를 담지한 금속 하니컴 및 그 제작방법에 관한 것으로, 구조는 간단하면서 전화능률이 뛰어나고 자동차(원동기관)의 배기유로나 기존의 자동차 머플러에 쉽게 장착할 수 있을 뿐만 아니라 자동차 배터리로 예열하여 시동초기에도 배기가스의 오염물질을 효과적으로 분해 및 제거할 수 있도록 한 것이다.The present invention supports a catalyst for the purification of exhaust gas for diesel and diesel vehicles, which effectively removes NOx, SOx, CO, unreacted hydrocarbons (HC), soot dust, etc. contained in exhaust gas of automobiles. A metal honeycomb and its manufacturing method are simple in structure and excellent in telephone efficiency and can be easily installed in an exhaust path of an automobile (drive engine) or an existing automobile muffler, as well as exhaust gas in the initial stage by starting with a car battery. It is to effectively decompose and remove pollutants.
현재 선진국의 대도시나 공장 밀집지역에서는 질소 산화물인 NO와 NO2와 같은 NOx의 발생량이 증가하고 있으므로 대기오렴에 대한 규제가 점차 강화되고 있으며, NOx의 주된 발생원인은 날마다 증가하는 자동차, 쓰레기 소각로, 화력발전소, 디젤 기관차, 선박, 각종 보일러 및 난방용 버너 등을 들 수 있다. 이 가운데 자동차의 매연이 대기 오염에 차지하는 비중은 75%에 달하고 있다.Since current NOx emissions, such as NO and NO 2, nitrogen oxides increased in the developed countries, large cities and factory areas and restrictions on waiting Come and strengthened gradually, the main cause of NOx cars, garbage incinerators, which increases day by day, Thermal power plants, diesel locomotives, ships, various boilers and heating burners. Among them, the smoke of automobile accounts for 75% of the air pollution.
디젤 자동차는 가솔린 자동차에 비하여 열효율이 좋고 높은 출력을 낼 수 있으나 비교적 공연비가 높은 영역에서 연소가 일어나고 있으므로 일산화탄소와 탄화수소의 배출량이 많아 휘발유 자동차의 배출가스 규제가 엄격하지 않았을 때에는 오염물질의 배출이 상대적으로 낮은 비교적 깨끗한 자동차로 알려졌었다.Although diesel cars have better thermal efficiency and higher output than gasoline cars, combustion occurs in a region with relatively high air-fuel ratios. As it was known as a low relatively clean car.
그러나 삼원촉매가 부착된 저공해 휘발유 자동차가 공급됨으로써 인체에 유독한 NOx 및 입자상 물질들이 많이 배출되는 디젤자동차가 큰 오염 배출원으로 등장하게 되었다. 따라서 디젤 자동차도 휘발유 자동차와 같이 배기가스 오염물질을 후처리하는 배기가스 정화기술을 개발하고 있다. 현재 개발되었거나 개발중인 디젤 자동차 매연 후 처리 장치는 다음 5가지로 분류할 수 있다.However, with the supply of low-polluting gasoline vehicles with three-way catalysts, diesel vehicles, which emit a lot of toxic NOx and particulate matter, have emerged as a large source of pollution. Accordingly, diesel cars are also developing exhaust gas purification technology to post-process exhaust pollutants like gasoline cars. Diesel vehicle soot post-treatment devices currently developed or under development can be classified into five categories:
1)경유 버너식 : 매연을 포집한 후 별도의 경유버너를 사용하여 재연소시키는 장치.1) Diesel burner type: A device that collects soot and reburns it using a separate diesel burner.
2)연료 첨가제식 : 연료에 암모니아, 우레아, 하이드라신 등의 첨가제를 주입하고 매연을 세라믹 필터로 포집한 후 전자장치로 재연소시키는 장치.2) Fuel additive type: A device that injects additives such as ammonia, urea, hydrazine, etc. into fuel, collects soot with ceramic filter, and re-burns with electronic device.
3)트랩-머플러식 : 머플러에 부착된 필터에 매연을 포집한 후 머플러에서 재연소시키는 장치.3) Trap-muffler type: A device that collects soot in the filter attached to the muffler and re-burns it in the muffler.
4)촉매식 : 촉매트랩을 설치하여 매연을 정화시키는 장치.4) Catalyst type: A device to purify soot by installing a catalyst trap.
5)저온 프라즈마식 : 저온 프라즈마 발생장치를 부착하여 매연을 분해시키는 장치.5) Low temperature plasma type: A device that decomposes smoke by attaching a low temperature plasma generator.
이들 가운데 경유 버너식은 엔진에 연결 부착하여야 하므로 엔진실에 별도의 설치공간이 필요하고, 연료 첨가제식은 머플러 앞에 별도의 전기장치와 세라믹 필터를 부착해야 하므로 역시 별도의 설치공간을 필요로 하는 단점을 지니고 있다.Of these, the diesel burner type requires a separate installation space in the engine room because it must be attached to the engine, and the fuel additive type requires a separate electric device and ceramic filter in front of the muffler. have.
트랩-머플러식은 현재 사용하고 있는 기존의 머플러를 제거하고 트랩-머플러로 교체해야 하는 단점을 지니고 있으며, 촉매식은 미반응탄화수소나 SOx에 의한 촉매독을 제거하기가 용이하지 못하여 정화효율이 떨어지는 단점을 지니고 있다. 그리고 저온 프라즈마식은 아크방전에 필요한 고전압 전원이 필요하므로 12V 자동차 배터리에 부착할 고전압 트랜스를 갖추어야 하므로 전력 과소비로 인한 에너지의 다량 소비로 연료비가 많이 드는 단점을 지니고 있다.The trap-muffler type has the disadvantage of removing the existing muffler currently used and replacing it with the trap-muffler. The catalyst type has a disadvantage in that the purification efficiency is not easy because it is not easy to remove the catalyst poison caused by unreacted hydrocarbons or SOx. I have it. In addition, low-temperature plasma type requires high voltage power required for arc discharge, and therefore has a high voltage transformer to be attached to a 12V car battery. Therefore, it has a disadvantage of high fuel cost due to large consumption of energy due to excessive power consumption.
이상 5가지 디젤 자동차 정화장치는 앞에서 언급한 바와 같이 각각의 뚜렷한 단점 외에도 모두 400만원대 이상의 고가 장비라는 공통의 단점을 지니고 있을 뿐만 아니라, 저온 프라즈마식을 제외하고는 자동차 시동 초기에는 정화장치의 온도가 낮아서 배기가스의 정화가 거의 이루어지지 않는다는 근본적인 단점을 지니고 있다.As mentioned above, all five diesel car purifiers have the common disadvantage that they are expensive equipment of more than 4 million won as well as their distinct disadvantages. It is low and has the fundamental disadvantage of hardly purifying exhaust gas.
본 발명에서는 원동기관의 배기가스 배출로에 열전도가 좋은 금속 하니컴을 설치하여 자동차 배터리 전원으로 예열토록 함으로서 시동초기에도 배기가스의 오염물질을 분해, 제거할 수 있도륵 하였으며, 두께가 얇은 3개의 하니컴 가운데 시동초기에는 3개의 하니컴을 동시에 예열하고, 자동차를 운행중일 때에는 제 1 단의 하니컴만 가열하여 미반응 탄화수소를 완전 연소시키도록 함으로써 미연소 탄화수소 입자에 의한 촉매오염을 막도록 하여 촉매의 분해능을 높인 것이 큰 장점이다.In the present invention, by installing a metal honeycomb with good thermal conductivity in the exhaust gas discharge path of the engine engine to preheat the car battery power, it is possible to decompose and remove the pollutants of the exhaust gas even at the beginning of the start, three thin honeycomb In the initial start-up, three honeycombs are preheated at the same time, and when the vehicle is in operation, only the honeycomb in the first stage is heated to completely burn unreacted hydrocarbons to prevent catalyst contamination by unburned hydrocarbon particles, thereby improving the resolution of the catalyst. It is a big advantage to increase.
뿐만 아니라, 담지된 금속 산화물이나 귀금속 촉매의 부착력을 최대한으로 향상시켜 촉매의 내구성을 높인것도 또 하나의 특징이며, 구조가 간편하고 머플러에 장착시 기존의 3원 촉매정도의 공간을 차지하므로 기존의 머플러에 구조변경없이 쉽게 장착할 수 있으며 동시에 가격도 다른 디젤 촉매의 절반이하로 낮출수 있는 장점도 지니고 있다.In addition, the durability of the catalyst is enhanced by improving the adhesion of the supported metal oxide or noble metal catalyst to the maximum. The structure is simple and it takes up about the space of the existing three-way catalyst when installed in the muffler. The muffler can be easily installed without structural changes, and at the same time, the price can be lowered to less than half of other diesel catalysts.
이와 같이 여러 가지 정점을 지닌 본 발명의 금속 하니컴 제작을 상세히 설명하면 다음과 같다.As described in detail the manufacture of the metal honeycomb of the present invention having various vertices as follows.
바나듐(V), 텅스텐(W), 몰리브덴(Mo) 금속분말을 1∼3(wt%), 티타늄(Ti) 분말은 10∼15(wt%), 그리고 알루미늄(Al) 분말은 10∼25(wt%) 그리고 철(Fe), 니켈(Ni), 크롬(Cr), 망간(Mn)의 비를 적당히 조절하여 전체 금속분말의 무게비를 100(wt%)로 하여 골고루 섞은다음 하니컴 구조로 성형되는 금형에 넣고, 바인더를 가하여 가압 성형하면 바인더가 완전 연소되고, 소결이 충분히 이루어지는 온도로 전기로나 가스로에서 소결하여 금속 하니컴(가)을 만든다.1 to 3 (wt%) of vanadium (V), tungsten (W) and molybdenum (Mo) metal powders, 10 to 15 (wt%) for titanium (Ti) powders, and 10 to 25 (for aluminum (Al) powders). wt%) and the ratio of iron (Fe), nickel (Ni), chromium (Cr) and manganese (Mn) is properly adjusted to make the weight ratio of the total metal powder 100 (wt%), and then evenly formed into a honeycomb structure. When put into a metal mold | die, the binder is added and pressure-molded, a binder is completely burned and it sinters in an electric furnace or a gas furnace at the temperature which fully sinters, and metal honeycomb is made.
이때 재료혼합을 균일하게 하기 위하여 앞에서 언급한 금속들의 일부나 전부를 이들 금속의 무기물이나 유기금화합물을 이용할 수 있다. 이렇게 만든 금속 하니컴(가)을 진한 염산, 황산, 질산과 같은 산용액에 담구어 합금속의 알미늄 성분을 용출시킨다. 이 경우 산의 농도와 담그는 시간에 따라 다른 금속보다 산화 전위가 큰 알미늄 금속을 쉽게 용출시킬 수 있게 된다. 이렇게 하여 금속 하니컴(가) 표면에 많은 홈과 기공을 만들 수 있게 된다.At this time, some or all of the above-mentioned metals may be used as inorganic materials or organogold compounds of these metals in order to make the material mixture uniform. The metal honeycomb (A) thus obtained is immersed in an acid solution such as concentrated hydrochloric acid, sulfuric acid, and nitric acid to elute the aluminum component in the alloy. In this case, it is possible to easily elute aluminum metal having a higher oxidation potential than other metals depending on the concentration of acid and the time of soaking. In this way, the metal honeycomb can make many grooves and pores on the surface.
이때 산용액에 담근 금속 하니컴(가)을 양극에 메달고 음극에는 비활성 전극을 대향전극으로 하여 전기분해시키면 알미늄 금속을 보다 효과적으로 용출시킬 수 있게 된다. 이렇게 산처리한 금속 하니컴을 염화백금산, 염화로듐산 및 염화팔라듐산 용액 각각이나 이들의 혼합 수용액에서 음극에 매달고 양극에는 백금과 같은 비활성 전극을 대향전극으로 하여 전기도금을 한다.At this time, the metal honeycomb (A) dipped in an acid solution is suspended on the anode and the inert electrode is used as the counter electrode in the cathode to electrolytically dissolve the aluminum metal. The acid-treated metal honeycomb is suspended from the chloroplatinic acid, rhodium chloride, and palladium chloride solution, or a mixed aqueous solution thereof, and is electroplated using an inert electrode such as platinum as the counter electrode.
이렇게 도금한 금속 하니컴(가)을 질산 산용액, 산소나 오존으로 버브링시키면서 양극에 매달고, 음극에는 백금을 대향전극으로 하여 전기분해시키면 금속하니컴 표면이나 기공 내부에 산화 바나듐(V2O5), 산화 텅스텐(WO3), 산화 모리브덴(MoO3)과 산화 티타늄(TiO2)등이 치밀하게 생성된다.The metal honeycomb plated in this way is suspended on the anode while bubbling with nitric acid solution, oxygen or ozone, and the cathode is electrolyzed using platinum as a counter electrode. Vanadium oxide (V 2 O 5 ) , Tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), titanium oxide (TiO 2 ), and the like are densely produced.
도 2는 본 발명 일 실시예를 도시한 단면도로, 금속 하니컴(가)은 배기가스가 통과할 수 있으면서 전원(B)으로 가열할 수 있게 도 3과 같이 벌집구조나 도 4와 같은 마름모꼴로 형성할 수 있을 것이다.2 is a cross-sectional view showing an embodiment of the present invention, the metal honeycomb (A) is formed in a honeycomb structure as shown in FIG. 3 or a rhombus as shown in FIG. 4 so that exhaust gas can pass and be heated by a power source (B). You can do it.
상기 하니컴은 경유 및 디젤 자동차(원동기관)의 배기가스 배출로(1)에 내식성 금속관체 또는 절연성 관체(2)를 설치하고, 관체(2) 내에 두께가 얇은 복수개의 금속 하니컴(4)(6)(8)을 소정거리로 이격시킨 다음 간격유지구(9)로 절연 유지되게 설치하고, 금속 하니컴(4)(6)(8)의 타측면에 전원 공급선(12)(14)를 각각 접속하여 하니컴(4)(6)(8)이 저항 발열되게 하고, 또한 선택 스위치(16)에 연결하여 금속 하니컴(4)(6)(8)에 가열전원(또는 예열전원)(B)을 선택적으로 공급할 수 있게 한다.The honeycomb is provided with a corrosion-resistant metal tube or an insulating tube (2) in the exhaust gas discharge path (1) of diesel and diesel vehicles (motive engine), a plurality of thin metal honeycomb (4) (6) in the tube (2) (8) are spaced apart by a predetermined distance and installed so as to be insulated and maintained by the spacing retainer (9), and the power supply lines (12) and (14) are respectively connected to the other side of the metal honeycomb (4) (6) (8). The honeycomb (4), (6), (8) is heated by resistance, and is connected to the selection switch (16) to selectively heat heating (or preheating power) (B) to the metal honeycomb (4) (6) (8). To be supplied.
본 발명에서 자동차(원동기관)를 시동할 때에나 시동 초기에는 오렴물질이 다량 배출되므로 1, 2, 3단 하니컴(4)(6)(8)을 동시에 가열하여 배기가스에 포함된 오염물직을 완전 분해, 제거하도록 하며, 운행중에는 오염물질이 비교적 적게 배출되므로 2단과 3단 하니컴(6)(8)은 사용하지 않고 1단 하니컴(4)만 사용하도록 함으로써 미반응 탄화수소가 제거되어 촉매독의 발생이 억제된다.In the present invention, when starting a car (drive engine) or at the beginning of the start, a large amount of unpleasant substances are discharged, thereby simultaneously heating the 1, 2, and 3
상기에서 자동차(원동기관)의 운행중에는 2단과 3단 하니컴(6)(8)은 별도의 선택 위치(SW)를 사용하여 원동기관을 시동할 때에만 약 30초 전후의 시간동안 가열되게 함으로써 배터리(B)의 과도한 소모성 방전을 방지하도록 하며, 선택 스위치(SW)와 2, 3단 하니컴(6)(8)의 전원공급선 사이에 대략 1분 전후의 시한 타이머(T)를 접속하여 선택 스위치(SW)를 계속 누르더라도 설정된 1분 전후의 시간이 경과하면 2, 3단 하니컴(6)(8)으로의 전원공급이 자동 차단되게 함으로써 배터리(B)의 소모성 방전을 방지하도록 함이 바람직하다.In the above, during operation of the automobile (motor engine), the 2nd and 3rd stage honeycomb 6 and 8 are heated for about 30 seconds only when starting the engine by using separate selection positions (SW). To prevent excessive consumable discharge of (B), the time switch (T) of about 1 minute is connected between the selector switch (SW) and the power supply line of the 2nd and 3rd stage honeycomb (6) (8), and the selector switch ( Even if SW is kept pressed, it is preferable to prevent power consumption of the battery B by automatically shutting off the power supply to the 2nd and
이렇게 만든 금속하니컴은 다음 식(1)과 식(2)에서 생성하는 NOx를 환원시켜 배기가스를 정화처리하게 된다.The metal honeycomb thus produced is purged of exhaust gas by reducing NOx generated in the following formulas (1) and (2).
자동차 배기가스는 초기에는 식(1)과 같이 일산화질소 가스, NO(g)로 생성되나 공기중의 산소와 쉽게 반응하여 식(2)와 같이 이산화질소가스, NO2(g)로 변한다. 이렇게 생성된 NO2(g)는 V2O5와 TiO2의 촉매작용에 의하여 다음 식(3)과 같이 환원되어 질소 (N2)와 산소(O2)로 분해되어 정화처리된다.Automotive exhaust gas is changed to initially formula (1), nitrogen monoxide gas, NO (g) but generated by the nitrogen dioxide gas as to readily react with oxygen in the air, Equation (2), NO 2 (g ) as follows. Thus produced NO 2 (g) is reduced by the catalytic action of V 2 O 5 and TiO 2 as shown in the following formula (3) is decomposed into nitrogen (N 2 ) and oxygen (O 2 ) and purified.
이때 촉매 V2O5와 TiO2는 SOx(SO2,SO3) 가스 생성을 촉진하기 때문에 SOx가스 생성을 억제하기 위하여 WO3와 MoO3촉매를 사용하게 된 것이다.At this time, since the catalysts V 2 O 5 and TiO 2 promote SOx (SO 2 , SO 3 ) gas generation, WO 3 and MoO 3 catalysts are used to suppress SOx gas generation.
백금(Pt)과 산화니켈(NiO) 촉매도 NO(g)를 환원시키는 촉매로 작용한다.Platinum (Pt) and nickel oxide (NiO) catalysts also act as catalysts to reduce NO (g).
그리고 이 촉매는 일산화 탄소(CO)를 완전 연소시키는 기능도 가지고 있다.The catalyst also has the ability to completely burn carbon monoxide (CO).
Pt와 NiO 촉매는 또한 미반응 탄화수소를 완전 연소시키는 역할도 한다.Pt and NiO catalysts also serve to completely burn unreacted hydrocarbons.
백금(Pt)과 팔라듐(Pd)은 수소(H2)를 산화시키는 촉매이다.Platinum (Pt) and palladium (Pd) are catalysts for oxidizing hydrogen (H 2 ).
니켈(Ni), 크롬(Cr), 철(Fe), 망간(Mn)과 같은 금속혼합 분말은 금속 하니컴 일부의 재료로 사용한 것은 자동차 배터리 전원을 금속 하니컴에 연결할때 하니컴이 발열체가 되어 미반응 탄화수소를 완전연소시키는 목적과 시동전 금속하니컴을 예열시켜 자동차 시동초기에도 자동차 배기가스의 오염물질을 효과적으로 분해 정화처리하기 위함이다.Metal-mixed powders such as nickel (Ni), chromium (Cr), iron (Fe), and manganese (Mn) are used as a part of the metal honeycomb, which means that the honeycomb becomes a heating element when the car battery is connected to the metal honeycomb. The purpose is to completely burn and to preheat the metal honeycomb before starting to effectively decompose and clean the pollutants in the car's exhaust gas even at the beginning of the car.
이상의 촉매반응에서 보는 바와 같이 본 발명에서 개발한 금속 하니컴은 디젤이나 경유 원동기관에서 다량 발생되는 NOx, SOx, CO, 미반응 탄화수소(예컨데, 옥탄 C8H18(g))와 같은 배기가스 매연의 오염물질을 효과적으로 제거하는 우수한 금속 하니컴이다.As can be seen from the above catalytic reaction, the metal honeycomb developed in the present invention is composed of exhaust gases such as NOx, SOx, CO, and unreacted hydrocarbons (for example, octane C 8 H 18 (g)) generated in diesel or diesel engines. It is an excellent metal honeycomb that effectively removes pollutants.
본 발명에서 금속 하니컴을 주로 경유 및 디젤 자동차(원동기관)에 사용하는 것으로 일예를 들었으나, 물론 가스버너나 석유버너, 보일러, 선박이나 디젤기관차, 소각로, 화력발전소 배기가스 정화장치 제작 또는 이방법을 이용한 석유나 가스를 이용한 난방, 주방기구 및 각종 건조기구등에 사용할 수 있음은 물론이다.In the present invention, the metal honeycomb is mainly used for diesel and diesel vehicles (motor engines), but of course, gas burners, oil burners, boilers, ships or diesel locomotives, incinerators, thermal power plant exhaust gas purification apparatuses or this method. Of course, it can be used for heating, kitchen utensils and various dryers using oil or gas.
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