EP0981402A1 - Auf gold basierender katalysator zur abgasreinigung - Google Patents

Auf gold basierender katalysator zur abgasreinigung

Info

Publication number
EP0981402A1
EP0981402A1 EP98918997A EP98918997A EP0981402A1 EP 0981402 A1 EP0981402 A1 EP 0981402A1 EP 98918997 A EP98918997 A EP 98918997A EP 98918997 A EP98918997 A EP 98918997A EP 0981402 A1 EP0981402 A1 EP 0981402A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
gold
oxides
catalyst according
support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98918997A
Other languages
English (en)
French (fr)
Inventor
Lachezar Angelov Petrov
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Laman Consultancy Ltd
Original Assignee
Laman Consultancy Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Laman Consultancy Ltd filed Critical Laman Consultancy Ltd
Publication of EP0981402A1 publication Critical patent/EP0981402A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • 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
    • B01J23/52—Gold
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention relates to a gold catalyst for the oxidation of carbon monoxide and hydrocarbons, reduction of nitrous oxides and the degradation of ozone.
  • a reduction of the emission of noxious gases from the combustion engines may be achieved by the use of PGM-based catalysts.
  • PGM-based catalysts function satisfactorily at temperatures higher than 300°C. Moisture and sulphur dioxide common for the exhaust gases, severely affect their performance at lower temperatures. It is known fact that 80% of the noxious gases from the combustion engine are emitted during the cold start of the engine, the first 3 to 5 minutes, where the conventional catalysts are not affective.
  • the PGM-based catalysts are even less effective for diesel vehicles where the temperature of the emitted gases in lower than the temperature of the exhaust gases from the gasoline passenger car. Conversion of the TPM, CO, HC and NOx (4-way catalyst) is considered a major challenge for diesel vehicle application in the future. Further, the high working temperatures of the PGM catalysts make them unsuitable for air purification in buildings, aircrafts and industrial sites.
  • Gold has been long regarded as far less catalytically active than the platinum group metals (PGM's). Recent publications in the literature have shown that gold, when highly dispersed on reducible oxides, can be active for low temperature oxidation of CO. However, gold containing catalysts as shown in the literature, ere either to costly, with gold concentration up to 12%, or show poor conversion at the higher flow rate of gases common for the working conditions. Thus, these catalysts are not suitable for industrial applications and do not have real commercial value.
  • German patent No. 3914294 describes a catalyst in which the gold is captured on an iron oxide-containing support which includes also alumina or aluminosilicate.
  • this catalyst has poor conversion of carbon monoxide at higher space velocity and is severely affected by moisture and sulphur dioxide.
  • gold catalysts supported on cobalt oxide, titanium oxide and iron oxide described in the literature are:
  • a catalyst for simultaneous oxidation and reduction reactions comprises a porous mixed oxides support having captured thereon a complex comprising gold and reducible oxide of a transition metal selected from chromium, copper, cobalt, manganese, iron or a combination of this metals.
  • concentration of the gold is from 0.1%-2.5%, preferably less than 1.5%, when the total concentration of the metals in the active component should not exceed 10% from the total mass of the catalyst.
  • the gold-reducible oxide complex contains chemical and physical bonding and is bonded to the mixed oxides support.
  • the support of the catalytic composition comprises individual or mixed oxides with a large surface area typically 80 m 2 /g to 400 m 2 /g.
  • Oxides composition is selected from ceria and titania oxides.
  • the concentration of ceria oxide is from 30-95% and of the titania oxide from 5-25%.
  • the catalyst may be in the form of powder, pellets, molded or deposited on a suitable carrier as foams, honeycombs (ceramics or metals).
  • the gold-transition metal oxide particles are deposited on the mixed oxides support by the methods of the known art: impregnation, precipitation, co- precipitation, wet incipient dryness, or a combination of these techniques.
  • the particles of the active component are finely dispersed throughout the support and should be of a size less than 40 nm, preferably less than 20 nm.
  • the pH of the process of preparation of gold-metal oxide catalyst is of significance and should be in the range of 7.0 to 12.0, preferably 8.0 to 10.5. The adjustment of the pH value in the prescribed range is achieved by the use of alkaline compound, for example, sodium or potassium carbonates, hydroxides or ammonia.
  • the catalyst is heated to a temperature in the range of 100°C to 500°C, to form fine cluster particles, immobilized on the surface of the support. The heating of the catalyst is maintained on oxidizing atmosphere or air.
  • the catalyst working temperature is from 0°C to 500°C.
  • the catalyst will have application also in the fuel cells technology.
  • the catalyst of the invention is more effective than similar catalyst of the prior art in the oxidation of carbon monoxide and hydrocarbons at law temperatures and in presence of moisture and sulphur dioxide;
  • the catalyst tolerates presence of sulphur dioxide
  • the catalyst has the ability for simultaneous reduction of nitrous oxides and oxidation of carbon monoxide and hydrocarbons at low and high temperature;
  • the catalyst is highly effective in the degradation of ozone at ambient temperature
  • the catalyst has high catalytic activities in the simultaneous oxidation of carbon monoxide, hydrocarbons and degradation of ozone at ambient temperature and presence of moisture; 7.
  • the catalyst could be used concurrently with the PGM catalysts to deal with their deficiency during the cold start of the combustion engine.
  • Figure 1 shows the bonding between gold and the reducible oxide of the transition metal, Co 2 0 3 in the active cluster, while Figure 2 shows the binding between the cluster and the oxides of the support.
  • Example 2 shows the bonding between gold and the reducible oxide of the transition metal, Co 2 0 3 in the active cluster, while Figure 2 shows the binding between the cluster and the oxides of the support.
  • Example 1 The catalyst obtained in Example 1 and a catalyst obtained in the same way, but with A1 2 0 3 support, are tested at various temperatures in a reactor containing 1 g of the catalyst, gas flow rate 45 000 h 1 and gas composition 1% CO, 0.9% 0 2 , 350 ppm C 3 H 6 , 350 ppm C 3 H 8 , 15 ppm S0 2 , humidity 95% and balance N 2 .
  • the results in Table 1 show the effect of the support on the activity of the gold catalyst in the oxidation of carbon monoxide and hydrocarbons.
  • the catalyst obtained by the method described in Example 1 is tested in a reactor containing 1 g of the catalyst at a temperature of 25°C, gas flow rate 360 000 h "1 and composition of the gas 25 ppm CO, the balance dry air and air with humidity 95%.
  • the catalyst obtained by the method described in Example 1 on the support of the invention and PGM catalyst on A1 2 0 3 support are tested in a reactor containing 1 g of the catalyst at temperature of 25°C, gas flow rate 60 000 h 1 and composition of the gas 1% CO, 0.9% 0 2 , 350 ppm C 3 H 6 , 350 ppm C 3 H 8 , 1000 ppm NOx, 15 ppm S0 2 , humidity 95% and the balance N 2 .
  • the catalyst obtained by the method described in Example 1 on the support of the invention is tested on a reactor containing 1 g of the catalyst at various temperatures, gas flow rate 60 000 h 1 and composition of the gas l%CO, 0.7- 0.9% 0 2 , 350 ppm C 3 H 6 , 350 ppm C 3 H 8 , 1000 ppm NOx, 15 ppm S0 2 , humidity 95% and the balance N 2 .
  • Table 4 are demonstrating the high activity of the catalyst of the invention, specifically at the cold start of the combustion engine.
  • the catalyst obtained by the method described in Example 1 is tested in a reactor containing 1 g of the catalyst at temperature 25°C, , gas flow rate 120 000 h "1 and gas composition 0.01% ozone and the balance air.
  • the catalyst obtained by the method described in Example 1 is tested in a reactor containing 1 g of the catalyst at temperature 25°C, , gas flow rate 120 000 h "1 and gas composition 0.01% ozone, 0.1% CO and the balance air.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
EP98918997A 1997-05-15 1998-05-15 Auf gold basierender katalysator zur abgasreinigung Withdrawn EP0981402A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BG101490A BG62687B1 (bg) 1997-05-15 1997-05-15 Златен катализатор за окисление на въглероден оксид и въглеводороди, редуциране на азотни оксиди иразлагане на озон
BG10149097 1997-05-15
PCT/BG1998/000010 WO1998051401A1 (en) 1997-05-15 1998-05-15 Gold based catalyst for exhaust gas purification

Publications (1)

Publication Number Publication Date
EP0981402A1 true EP0981402A1 (de) 2000-03-01

Family

ID=3927016

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98918997A Withdrawn EP0981402A1 (de) 1997-05-15 1998-05-15 Auf gold basierender katalysator zur abgasreinigung

Country Status (5)

Country Link
EP (1) EP0981402A1 (de)
JP (1) JP2001524030A (de)
AU (1) AU7201398A (de)
BG (1) BG62687B1 (de)
WO (1) WO1998051401A1 (de)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BG62723B1 (bg) * 1997-09-29 2000-06-30 "Ламан-Консулт"Оод Златен катализатор и приложението му при горивниелементи
GB2357628A (en) * 1998-09-07 2001-06-27 Anglo American Res Lab Gold catalyst for fuel cell
CA2368378A1 (en) * 1999-04-01 2000-10-12 Bojidara Grigorova Selective catalytic oxidation of co in presence of h2
US7243658B2 (en) 2003-06-13 2007-07-17 Philip Morris Usa Inc. Nanoscale composite catalyst to reduce carbon monoxide in the mainstream smoke of a cigarette
US9107452B2 (en) 2003-06-13 2015-08-18 Philip Morris Usa Inc. Catalyst to reduce carbon monoxide in the mainstream smoke of a cigarette
US7152609B2 (en) 2003-06-13 2006-12-26 Philip Morris Usa Inc. Catalyst to reduce carbon monoxide and nitric oxide from the mainstream smoke of a cigarette
US7165553B2 (en) 2003-06-13 2007-01-23 Philip Morris Usa Inc. Nanoscale catalyst particles/aluminosilicate to reduce carbon monoxide in the mainstream smoke of a cigarette
US7712471B2 (en) 2003-10-27 2010-05-11 Philip Morris Usa Inc. Methods for forming transition metal oxide clusters and smoking articles comprising transition metal oxide clusters
US7677254B2 (en) 2003-10-27 2010-03-16 Philip Morris Usa Inc. Reduction of carbon monoxide and nitric oxide in smoking articles using iron oxynitride
US20050197244A1 (en) * 2004-03-05 2005-09-08 L'vovich Moroz B. Exhaust treatment system and catalyst system
US7569510B2 (en) * 2006-02-27 2009-08-04 Philip Morris Usa Inc. Catalysts to reduce carbon monoxide such as in the mainstream smoke of a cigarette
CZ301720B6 (cs) * 2008-10-17 2010-06-02 Univerzita Karlova V Praze Katalyzátor na bázi kov-CeO2 pro použití obzvlášte v palivových cláncích a zpusob jeho prípravy
JP5821254B2 (ja) * 2011-04-13 2015-11-24 トヨタ自動車株式会社 排ガス浄化用触媒
US8668890B2 (en) * 2012-04-26 2014-03-11 Basf Corporation Base metal catalyst composition and methods of treating exhaust from a motorcycle
US8765085B2 (en) 2012-04-26 2014-07-01 Basf Corporation Base metal catalyst and method of using same
WO2014010012A1 (ja) 2012-07-09 2014-01-16 トヨタ自動車株式会社 排ガス浄化用触媒及びその製造方法
JP6107487B2 (ja) * 2013-07-09 2017-04-05 株式会社豊田中央研究所 Ｎ２ｏ分解触媒及びそれを用いたｎ２ｏ含有ガスの分解方法
JP6154409B2 (ja) * 2015-01-27 2017-06-28 トヨタ自動車株式会社 Ｎｉ及びＡｕを含有する異種金属多核錯体の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0723931A1 (de) * 1995-01-25 1996-07-31 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren zur Entfernung von Verunreinigungen aus einer gasförmigen Verbindung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1581628A (en) * 1976-03-18 1980-12-17 Johnson Matthey Co Ltd Catalytic purification of automobile exhaust gases
JPH02290251A (ja) * 1989-01-24 1990-11-30 Nkk Corp 接触燃焼用金含有触媒
IL108635A (en) * 1993-02-18 1997-09-30 Grigorova Bojidara Catalyst for use in an oxidation reaction
IL112414A (en) * 1994-01-25 1998-08-16 Anglo American Res Lab Pty Ltd Method of preparing a catalyst by impregnating a porous support with a solution
BR9508049A (pt) * 1994-06-17 1997-08-12 Bojidara Grigorova Catalisador
ES2132728T3 (es) * 1994-11-02 1999-08-16 Anglo American Res Lab Pty Ltd Catalizador con soporte de oxido de zirconio/oxido de cerio.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0723931A1 (de) * 1995-01-25 1996-07-31 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren zur Entfernung von Verunreinigungen aus einer gasförmigen Verbindung

Also Published As

Publication number Publication date
BG62687B1 (bg) 2000-05-31
WO1998051401A1 (en) 1998-11-19
AU7201398A (en) 1998-12-08
JP2001524030A (ja) 2001-11-27
BG101490A (en) 1999-04-30

Similar Documents

Publication Publication Date Title
CA1247074A (en) Three-way catalysts of improved efficiency
CA2044984C (en) Catalyst for purifying exhaust gas from diesel engines
WO1998051401A1 (en) Gold based catalyst for exhaust gas purification
CA1115681A (en) Poisoning-resistant gas conversion catalysts and processes for making and using the same
EP0171151B1 (de) Dreiwegkatalysator für magere Auspuffsysteme
US6172000B1 (en) Diesel catalyst made from a mixture of particles: platinum on alumina and manganese-zirconium oxide
US5286699A (en) Exhaust gas purifying catalyst suppressing the generation of hydrogen sulfide and method of making the catalyst
KR100319922B1 (ko) 디젤엔진 배기가스 정화용 촉매
US6685899B1 (en) Catalyst and method for purifying exhaust gas from vehicle engines
KR100213183B1 (ko) 자동차 배기가스 정화용 촉매 및 그 제조방법
JPWO2012096039A1 (ja) 脱硝触媒組成物、及びそれを用いた脱硝方法
JPH0884911A (ja) 窒素酸化物分解用触媒およびこれを用いたディーゼルエンジン排ガスの浄化方法
WO1993020937A1 (en) Device for cleaning exhaust fumes
CA1333385C (en) Exhaust gas purifying catalyst suppressing the generation of hydrogen sulfide
JP3764760B2 (ja) リーンバーンエンジンからの排気ガスを浄化するための触媒および浄化方法
JPH09225264A (ja) 排気ガス浄化用触媒
JPS61209045A (ja) 排ガス浄化用触媒
JP4301348B2 (ja) 窒素酸化物分解用触媒およびこれを用いたディーゼルエンジン排ガスの浄化方法
JPH06198178A (ja) 排気ガス浄化用触媒
JPH0557191A (ja) デイーゼルエンジンの排気浄化用触媒
JP3473245B2 (ja) 排気ガス浄化用触媒
JPH10211431A (ja) ディーゼル排ガス用酸化触媒
JPH05138026A (ja) デイーゼルエンジンの排気浄化用触媒
JPH06190279A (ja) 排気ガス浄化用触媒
WO2026058331A1 (ja) 排気ガス浄化触媒

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991214

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20010709

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20021203