WO2006094720A1 - Verfahren zum herstellen eines katalytisch wirkenden minerals auf basis eines gerüstsilikates - Google Patents
Verfahren zum herstellen eines katalytisch wirkenden minerals auf basis eines gerüstsilikates Download PDFInfo
- Publication number
- WO2006094720A1 WO2006094720A1 PCT/EP2006/001957 EP2006001957W WO2006094720A1 WO 2006094720 A1 WO2006094720 A1 WO 2006094720A1 EP 2006001957 W EP2006001957 W EP 2006001957W WO 2006094720 A1 WO2006094720 A1 WO 2006094720A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal salt
- silicate
- framework silicate
- treated
- dried
- Prior art date
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/208—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the invention relates to a process for preparing a catalytically active mineral based on a framework silicate, after which the framework silicate is first treated with a metal salt solution and then dried.
- DE 43 04 821 A1 describes a process for modifying molecular sieves or zeolites by means of ion exchange.
- those of a metal from the first to the eighth subgroup of the periodic table in the form of a salt or oxide are used.
- the zeolite used is subjected to multiple ion exchange in aqueous suspension with a large excess of NH 4 NO 3 solution. Subsequently, a calcination at about 550 ° C (see Example 1).
- US 2003/0165415 A1 has disclosed a process for the catalytic reduction of nitrogen oxides in exhaust gases.
- a catalyst or catalyst base material of the aluminum silicate type which is treated with a transition metal in aqueous solution.
- DE 196 37 032 A1 deals with a method for removing nitrogen oxides from lean exhaust gases.
- a catalyst is prepared in which a zeolite is brought into contact with a metal salt which is in the solid state, and then the metal salt is reduced to the corresponding metal.
- the introduction of the metal into the zeolite takes place via a solid-state reaction in which the zeolite is intimately mixed with the metal salt or a metal salt mixture, for example in a ball mill. Details on the pretreatment of the zeolites remain open.
- the invention is based on the technical problem of further developing a process for preparing a catalytically active mineral based on a framework silicate of the embodiment described above in such a way that a catalyst base material which is as emission-free as possible is provided which has an increased service life and if possible simple, inexpensive and procedurally unproblematic manufacture.
- the invention provides a generic method for producing a catalytically active mineral based on a framework silicate for use as catalyst base material in the catalytic emission control in particular automobiles, after which the framework silicate is first treated with a metal salt solution and then dried, and then the dried framework silicate is treated in the hydrogen form with a metal salt in particular transition metal based in the course of a solid-state ion exchange.
- the transition metal-based metal salt is preferably copper-based and / or iron-based.
- the invention particularly preferably uses a natural mineral in the framework silicate and in particular natural zeolite-type minerals, preferably those of the heulandite group, very particularly preferably clinoptilolites.
- the preferred zeolites used are also referred to as so-called "molecular sieves”.
- In natural zeolites about 45 structures are known, depending on the mining towns, from which they are derived and depending on the zeolite type in question, different amounts of alkaline earths and alkalis, such as calcium, magnesium or potassium ions. Depending on the type, these cations change the entry pores to the described internal cavities of the silicon-aluminum crystal lattice of the relevant framework silicate. It has basically been found that natural minerals and in particular the natural zeolite is thermally more stable than, for example, synthetic zeolite.
- natural zeolites have a special texture with meso- and macropores that are not observed in synthetic zeolites.
- the aforementioned texture allows the adsorption of organic compounds whose radii are larger than the inlet channels of the micropores also present in synthetic zeolites.
- this texture is believed to be responsible for the increased thermal stability of natural versus synthetic zeolite.
- the catalytically active mineral prepared by the process according to the invention in particular based on a natural zeolite, is thermally stable up to temperatures of 500 ° C. or even more, and Conversion rates of NO x in nitrogen provides that are located even in this area well above 50 vol .-%. Ie. more than 50% by volume of NO x is converted into nitrogen.
- the natural zeolite used contains more than 50% by weight, preferably more than 70% by weight, in particular more than 80% by weight and particularly preferably more than 90% by weight.
- Clinoptilolite contains.
- Clinoptilolite is an aluminum silicate which reacts anionically and, due to its lattice structure and the high internal and external surface area and porosity, is responsible for ion exchange with cations and also as absorber for liquids and absorber / adsorber for gases and special catalytic effects features.
- the framework silicate used according to the invention is predominantly a natural mineral, in particular natural zeolite, it is of course possible to use chabazite, mordenite, etc., or mixtures thereof, in addition to clinoptilolite in principle.
- the framework silicate used contains at least 45% by weight of natural zeolite, in particular more than 75% by weight and particularly preferably more than 80% by weight.
- the remainder of the framework silicate used can be formed, for example, by artificial zeolites, which, however, always occupy a lower proportion by weight than the natural zeolites.
- by weight and preferably natural zeolite predominates, so that the advantages described above (different pore diameters and high thermal stability) are established in each case.
- the natural zeolite used is mainly the already mentioned heulandite and in particular clinoptilolite, which in each case represents the main constituent of the natural zeolite.
- an ammonium chloride / ammonium nitrate or the like solution in particular based on ammonium, is predominantly used.
- the predominantly used natural zeolite not only undergoes purification, but is also converted into the desired hydrogen form.
- ammonium ions replace NH 4 single cations in the framework silicate or the natural zeolite, for example calcium or sodium ions.
- the treatment with the metal salt solution or the ammonium chloride takes place predominantly at room temperature or at elevated temperatures up to about 60 ° C.
- the mixing ratio provides that usually more than 50 g, preferably more than 100 g and particularly preferably up to about 300 g of framework silicate or natural zeolite per liter of metal salt solution are used, wherein water is usually used as the solvent.
- the direct use of fuel as a reducing agent is conceivable, for example, in diesel engines in addition, the diesel fuel is injected directly into a thus equipped catalyst. This is usually not necessary in the case of Otto engine internal combustion engines, because in this case the exhaust gas itself contains a quantity of hydrocarbon sufficient for the NO x reduction.
- the described drying process of the framework silicate treated with the metal salt solution in the hydrogen form is followed by Treatment with a transition metal-based or copper-based metal salt and / or iron-based in the course of a solid-state ion exchange.
- This can be explicitly dispensed with an acid treatment with the negative consequences outlined above in contrast to the prior art. Rather, there is a further ion exchange of the cations in the cavities of the framework silicate (in addition to their already occurred partial exchange against ammonium or hydrogen ions), by predominantly copper atoms and / or iron atoms in the dry phase.
- Such a solid-state ion exchange is known in principle, for which reference is made to the article by M. Crocker et al.
- the copper atoms and / or iron atoms incorporated in the second ion exchange are, in the example case, capable of penetrating into the interior of the said cavities (because they are not surrounded by a large-volume hydrate shell) due to the solid-state reaction associated therewith.
- the dried framework silicate in the hydrogen form for example, dry mixed with copper nitrate and optionally ground and then subjected to a drying process. It is usually worked with a shock-like temperature increase, starting at about 100 ° C up to about 500 ° C (or even above). For example, the 100 ° C can be reached in about 10 minutes. Ie. the temperature gradient is about 10 ° C / min. or more in the described shock-like temperature increase.
- the copper atoms or, in general, transition metal ions of, for example, titanium, iron, cobalt, nickel or zinc are able to replace the cations present in the framework silicate, such as calcium, sodium or potassium ions, at least in part.
- the framework silicate thus treated can still be calcined, it being understood that the drying process and the calcination, ie the removal of any water of crystallization or of solvents, can also be combined. At the same time undergoes by this process carbon dioxide cleavage. In addition, the unchanged potassium ions ensure thermal stabilization.
- the mainly embedded copper cations or iron cations in the respective intermediate layer or largely in the interior of the cavities are capable of the particularly disturbing nitrogen oxides NO x at elevated temperature substantially in nitrogen (N 2 ) and oxygen (O 2 ) split up.
- mainly copper or iron or in general a transition metal which is present in the treated ' framework silicate usually to more than 0.1 wt .-% and in particular in a concentration of more than 1, 0 wt .-% and particularly preferably in a range of 1, 5 to 2.5 wt .-%, in any case usually less than 5 wt .-%, not only the desired catalytic effect is achieved, but this is based on a non-toxic and at the temperatures reached volatile metal.
- the procedure described for example, by mixing copper nitrate (iron nitrate) dry with the framework silicate in hydrogen form, optionally grinding and heating, it is also possible to use a metal solution, for example copper nitrate solution or the like.
- concentration of the solution compared to the thus treated and previously dried scaffold silicate is adjusted so that the treated dried scaffold silicate after treatment has comparable moisture levels as in the natural state. That is, the upstream drying process after the reaction with the metal salt solution is performed in this case so that the natural moisture content of the framework silicate of, for example, 10 wt .-% to 20 wt .-% is well below and by the subsequent treatment with the copper solution ( Iron solution) is reached again in about. The subsequent calcining in both cases then causes any remaining solvents to be removed. That is, the copper solution is used in such a way that the dried framework silicate remains dry in the hydrogen form to a lying in the range of natural moisture content of water.
- the transition metal-based metal salt usually contains more than 50% by weight of copper and / or iron.
- the metal solution or copper solution or iron solution can be used as complementary mixture components. That is, it is conceivable to dry-mix the framework silicate with, for example, a mixture of copper nitrate and zinc sulfate and to heat it up abruptly as described.
- the copper nitrate solution described can be used in conjunction with a zinc chloride solution in the example as an alternative.
- the catalytically active mineral or natural zeolite produced in this way can be brought into any desired shape. It can by the simple Addition of water to the powder produced a self-binding effect can be achieved. That is, the thus prepared mineral can be extruded, for example, in any shape or even applied as a coating on a catalyst base material. A special binder is not required, so that any negative effects of this binder on the selectivity of the catalytic effect are not observed.
- the framework silicate is ground before the treatment, wherein it has proven useful if 90% of the particles thus produced has a particle size of less than 1 mm, especially one of less than 250 microns and preferably below 25 microns, and most preferably of less than 5 microns.
- the fineness exerts a not insignificant influence on the previously described conversion rate. This conversion rate indicates how much weight percent of NO x in the exhaust gas is converted to nitrogen.
- a catalytically active material can be made available as catalyst base material for catalytic exhaust gas purification in particular automobiles by a simple physical chemical process, which not only successfully converts NOx into nitrogen, but is also active in comparison with the prior art significantly widened temperature range, ranging from about 150 ° C up to about 700 ° C.
- PGM metals that is, those of the platinum group.
- the associated limitations are overcome, with a marked increase in resistance to water and a particular selectivity for the conversion of NO x into nitrogen.
- Another advantage of a catalyst prepared in this way is that the DeNO x reaction works with both ammonium and hydrocarbons. Due to the high selectivity, cyanates or similar toxic gases are not produced. In addition, there is no danger of ammonia slip, that is the Breakthrough of free NH 3 through the catalyst, which due to the toxicity of ammonia is absolutely to be avoided.
- the invention also relates to a catalyst which is used on the basis of the catalytically active mineral prepared by the process described as catalyst base material, in particular in motor vehicles and here for exhaust gas purification.
- the catalytically active mineral described can also be combined with a catalytically active layer silicate whose intermediate layer has supporting metal atom pillars and has metal atoms embedded in the intermediate layer, in particular so-called pillard clays.
- combinations of a two-part catalytically active shaped body comprises, in which one shaped body as a catalyst on the scaffold silicate or zeolite described, while the other shaped body designed as a so-called Pillard Clay according to WO 2004/030817 A2 is.
- a particularly advantageous catalytic effect in particular in the sense of a pronounced selectivity for the conversion into nitrogen, is achieved.
- the pillar clay body is active especially in the low temperature range, whereas the zeolite based catalyst mainly covers the higher temperature range.
- the catalyst base material produced by the process described that predominantly no synthetic materials are used, but mainly inexpensive natural minerals and in particular natural zeolite.
- the cleaning process with the metal salt solution takes place predominantly at room temperature or only slightly increased temperatures, and is therefore particularly energy-efficient.
- the described flexible ion exchange takes place as it were two stages as described, due to the solid-state ion exchange without harmful wastewater. Because costly metals are dispensed with for the catalytic effect and in contrast cheap transition metals are used, the preparation of the catalyst base material is particularly inexpensive. Nevertheless, there is a high selectivity in the catalytic effect. In addition, a broad temperature range is covered so that the described catalyst base material is suitable for both low and high temperature applications. Here are the main benefits.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0608072-3A BRPI0608072A2 (pt) | 2005-03-05 | 2006-03-03 | processo para preparação de um mineral cataliticamente ativo com base em um silicato tectÈnico |
US11/885,692 US20080193358A1 (en) | 2005-03-05 | 2006-03-03 | Method for the Production of a Catalytically Active Mineral on the Basis of a Tectosilicate |
JP2007557435A JP2008531267A (ja) | 2005-03-05 | 2006-03-03 | 骨格シリケートを基礎とし触媒的に作用する鉱物の製造方法 |
EP06723201A EP1858643A1 (de) | 2005-03-05 | 2006-03-03 | Verfahren zum herstellen eines katalytisch wirkenden minerals auf basis eines gerüstsilikates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005010221.2 | 2005-03-05 | ||
DE102005010221A DE102005010221A1 (de) | 2005-03-05 | 2005-03-05 | Verfahren zum Herstellen eines katalytisch wirkenden Minerals auf Basis eines Gerüstsilikates |
Publications (2)
Publication Number | Publication Date |
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WO2006094720A1 true WO2006094720A1 (de) | 2006-09-14 |
WO2006094720B1 WO2006094720B1 (de) | 2007-03-15 |
Family
ID=36250903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/001957 WO2006094720A1 (de) | 2005-03-05 | 2006-03-03 | Verfahren zum herstellen eines katalytisch wirkenden minerals auf basis eines gerüstsilikates |
Country Status (10)
Country | Link |
---|---|
US (1) | US20080193358A1 (de) |
EP (1) | EP1858643A1 (de) |
JP (1) | JP2008531267A (de) |
KR (1) | KR20070114804A (de) |
CN (1) | CN101163548A (de) |
BR (1) | BRPI0608072A2 (de) |
DE (1) | DE102005010221A1 (de) |
RU (1) | RU2007136844A (de) |
WO (1) | WO2006094720A1 (de) |
ZA (1) | ZA200708529B (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007001466A1 (de) | 2007-01-10 | 2008-07-17 | S&B Industrial Minerals Gmbh | Verfahren zur Herstellung eines antibakteriell bzw. antimikrobiell wirkenden keramischen Werkstoffes sowie dessen Verwendung |
DE102007018170A1 (de) | 2007-04-18 | 2008-10-30 | S&B Industrial Minerals Gmbh | Verfahren zur Ausrüstung eines vorzugsweise porösen keramischen Trägermaterials mit einem Wirkstoff |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK3300791T3 (da) * | 2007-04-26 | 2019-06-11 | Johnson Matthey Plc | Overgangsmetal/zeolit-scr-katalysatorer |
GB201705279D0 (en) | 2017-03-31 | 2017-05-17 | Johnson Matthey Plc | Selective catalytic reduction catalyst |
GB201705289D0 (en) | 2017-03-31 | 2017-05-17 | Johnson Matthey Catalysts (Germany) Gmbh | Selective catalytic reduction catalyst |
GB201900484D0 (en) | 2019-01-14 | 2019-02-27 | Johnson Matthey Catalysts Germany Gmbh | Iron-loaded small pore aluminosilicate zeolites and method of making metal loaded small pore aluminosilicate zeolites |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3689212A (en) * | 1968-12-27 | 1972-09-05 | Air Liquide | Method of purifying gaseous mixtures |
DE2443899A1 (de) * | 1973-09-13 | 1975-04-03 | Kaihatsu Kenkyusho Ind Res | Reduktionskatalysator zur abscheidung von stickoxiden aus abgasen |
GB2039863A (en) * | 1979-01-12 | 1980-08-20 | Norton Co | Catalytic reduction of oxides of nitrogen by ammonia in presence of modified clinoptilolite |
JPH02149317A (ja) * | 1988-11-29 | 1990-06-07 | Ind Res Inst Japan | 廃煙中の窒素酸化物除去法 |
US5451385A (en) * | 1991-08-01 | 1995-09-19 | Air Products And Chemicals, Inc. | Control of exhaust emissions from methane-fueled internal combustion engines |
US5695728A (en) * | 1993-06-25 | 1997-12-09 | Tosoh Corporation | Method for removal of nitrogen oxides |
US20030165415A1 (en) * | 1999-10-28 | 2003-09-04 | Ott Kevin C. | Catalysts for lean burn engine exhaust abatement |
WO2004030817A2 (de) * | 2002-09-30 | 2004-04-15 | Iko Minerals Gmbh | Verfahren zur herstellung von katalytisch wirkende schichtsilikaten |
WO2005092499A1 (de) * | 2004-03-17 | 2005-10-06 | Gm Global Technology Operations, Inc. | KATALYSATOR ZUR VERBESSERUNG DER WIRKSAMKEIT DER NOx-REDUKTION IN KRAFTFAHRZEUGEN |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07106300B2 (ja) * | 1989-12-08 | 1995-11-15 | 財団法人産業創造研究所 | 燃焼排ガス中の窒素酸化物除去法 |
DE4304821A1 (de) * | 1993-02-17 | 1994-08-18 | Degussa | Verfahren zum Modifizieren von Molekularsieben mittels Ionenaustausch |
DE19637032A1 (de) * | 1996-09-12 | 1998-03-19 | Volkswagen Ag | Verfahren zum Entfernen von Stickstoffoxiden aus mageren Abgasen |
-
2005
- 2005-03-05 DE DE102005010221A patent/DE102005010221A1/de not_active Withdrawn
-
2006
- 2006-03-03 JP JP2007557435A patent/JP2008531267A/ja not_active Withdrawn
- 2006-03-03 CN CNA2006800137046A patent/CN101163548A/zh active Pending
- 2006-03-03 BR BRPI0608072-3A patent/BRPI0608072A2/pt not_active Application Discontinuation
- 2006-03-03 RU RU2007136844/04A patent/RU2007136844A/ru not_active Application Discontinuation
- 2006-03-03 ZA ZA200708529A patent/ZA200708529B/xx unknown
- 2006-03-03 KR KR1020077022711A patent/KR20070114804A/ko not_active Application Discontinuation
- 2006-03-03 EP EP06723201A patent/EP1858643A1/de not_active Withdrawn
- 2006-03-03 WO PCT/EP2006/001957 patent/WO2006094720A1/de active Application Filing
- 2006-03-03 US US11/885,692 patent/US20080193358A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US3689212A (en) * | 1968-12-27 | 1972-09-05 | Air Liquide | Method of purifying gaseous mixtures |
DE2443899A1 (de) * | 1973-09-13 | 1975-04-03 | Kaihatsu Kenkyusho Ind Res | Reduktionskatalysator zur abscheidung von stickoxiden aus abgasen |
GB2039863A (en) * | 1979-01-12 | 1980-08-20 | Norton Co | Catalytic reduction of oxides of nitrogen by ammonia in presence of modified clinoptilolite |
JPH02149317A (ja) * | 1988-11-29 | 1990-06-07 | Ind Res Inst Japan | 廃煙中の窒素酸化物除去法 |
US5451385A (en) * | 1991-08-01 | 1995-09-19 | Air Products And Chemicals, Inc. | Control of exhaust emissions from methane-fueled internal combustion engines |
US5695728A (en) * | 1993-06-25 | 1997-12-09 | Tosoh Corporation | Method for removal of nitrogen oxides |
US20030165415A1 (en) * | 1999-10-28 | 2003-09-04 | Ott Kevin C. | Catalysts for lean burn engine exhaust abatement |
WO2004030817A2 (de) * | 2002-09-30 | 2004-04-15 | Iko Minerals Gmbh | Verfahren zur herstellung von katalytisch wirkende schichtsilikaten |
WO2005092499A1 (de) * | 2004-03-17 | 2005-10-06 | Gm Global Technology Operations, Inc. | KATALYSATOR ZUR VERBESSERUNG DER WIRKSAMKEIT DER NOx-REDUKTION IN KRAFTFAHRZEUGEN |
Non-Patent Citations (1)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 014, no. 397 (C - 0752) 28 August 1990 (1990-08-28) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007001466A1 (de) | 2007-01-10 | 2008-07-17 | S&B Industrial Minerals Gmbh | Verfahren zur Herstellung eines antibakteriell bzw. antimikrobiell wirkenden keramischen Werkstoffes sowie dessen Verwendung |
EP1952692A1 (de) | 2007-01-10 | 2008-08-06 | S & B Industrial Minerals GmbH | Verfahren zur Herstellung eines antibakteriell bzw. antimikrobiell wirkenden keramsichen Werstoffes sowie dessen Verwendung |
DE102007018170A1 (de) | 2007-04-18 | 2008-10-30 | S&B Industrial Minerals Gmbh | Verfahren zur Ausrüstung eines vorzugsweise porösen keramischen Trägermaterials mit einem Wirkstoff |
DE102007018170B4 (de) * | 2007-04-18 | 2010-09-23 | S & B Industrial Minerals Gmbh | Verfahren zur Ausrüstung eines vorzugsweise porösen keramischen Trägermaterials mit einem Wirkstoff |
Also Published As
Publication number | Publication date |
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JP2008531267A (ja) | 2008-08-14 |
CN101163548A (zh) | 2008-04-16 |
RU2007136844A (ru) | 2009-04-10 |
US20080193358A1 (en) | 2008-08-14 |
ZA200708529B (en) | 2009-03-25 |
WO2006094720B1 (de) | 2007-03-15 |
DE102005010221A1 (de) | 2006-09-07 |
EP1858643A1 (de) | 2007-11-28 |
KR20070114804A (ko) | 2007-12-04 |
BRPI0608072A2 (pt) | 2009-11-03 |
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