CN102665905A - Age-resistant Rh-zeolite catalyst - Google Patents

Age-resistant Rh-zeolite catalyst Download PDF

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Publication number
CN102665905A
CN102665905A CN201080052490XA CN201080052490A CN102665905A CN 102665905 A CN102665905 A CN 102665905A CN 201080052490X A CN201080052490X A CN 201080052490XA CN 201080052490 A CN201080052490 A CN 201080052490A CN 102665905 A CN102665905 A CN 102665905A
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constituent
rhodium
catalysis constituent
catalysis
catalyst
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A·蒂斯勒
F·克洛斯
M·哈特
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Sued Chemie AG
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    • 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
    • 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
    • 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
    • B01J29/068—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B01J35/56—
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0248—Coatings comprising impregnated particles
    • 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
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/912—HC-storage component incorporated in the catalyst
    • 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

Abstract

The invention relates to a catalytic composition comprising a porous carrier material and rhodium, wherein the rhodium is substantially located in the pores of the porous carrier material. The invention further relates to a method for producing the catalytic composition according to the invention containing rhodium, to the use of the catalytic composition as a NOx-reduction catalyst and hydrocarbon store, and to a catalyst component comprising the catalytic composition according to the invention.

Description

Anti-aging rhodium-zeolite catalyst
The present invention relates to comprise the catalysis constituent of porous carrier materials and rhodium, wherein rhodium is arranged in the hole of porous carrier materials in fact.The invention still further relates to the method that is used to prepare according to catalysis constituent of the present invention, this catalysis constituent as NO xReducing catalyst is with the purposes of storing up the hydrocarbon thing and comprise the catalyst structure according to catalysis constituent of the present invention.
Three-way catalyst is used to remove petrolic waste gas for a long time.Their great majority comprise platinum, rhodium and have the metal oxide such as the cerium oxide of storage oxygen function.Platinum is responsible for oxidation reaction, thereby is responsible for carbon monoxide (CO) and hydrocarbon (HC) are oxidized to CO 2And H 2O.Rhodium is responsible for nitrogen oxide (NO x) be reduced to nitrogen (N 2).
Three-way catalyst works near the waste gas constituent of fluctuation λ=1 usually.This means ideally, just the same many oxidation (NO are arranged in waste gas x, O 2) and reduction (CO, HC) gas.Because this can not always be able to accurately guarantee that cerium oxide provides storage oxygen capacity (OSC), it is (CeO under oxidizing condition 2Form) loading oxygen also can be at (Ce under the reducing condition 2O 3Form) release oxygen once more.
The carried catalyst that loading is used for the noble metal of aforementioned applications prepares by means of multi-stage process usually.For example, in first step, carrier material is with the precious metal salt solution dipping of needed noble metal.In subsequently step after carrier material is removed solvent, calcinated support material in another step, wherein noble metal can be converted into oxide form through heat treatment.Under many situations, oxide form has been the catalytic activity kind, so catalyst can this form use.In addition, maybe be in another step for example by means of hydrogen, carbon monoxide or wet-chemical reducing agent oxide form be converted into the noble metal that oxidation state is 0 high degree of dispersion, it also can be used as the catalytic activity kind.
Known carrier noble metal catalyst loses the activity of a great deal of being exposed to heat-flash following time of loading.Activity of such catalysts is disperseed directly related with metal.Because thermal stress, the metallic particles sintering is on the surface of catalyst carrier, and is big more, and the ergophore of formation is few more.The activity of carrier metal catalyst depends on the size of metallic particles usually.The speed of this so-called heat ageing process depends on the temperature levels when using catalyst.Exactly, along with operating temperature increases, the speed of ageing process also increases, and this is increased by the flowability of the metallic particles on the surfaces of carrier materials under higher temperature and follows the sintering increase and cause.This is undesirable.
DE 10 2,007 003 533 A1 disclose a kind of catalyst that comprises porous carrier materials and zeolitic material, load metallic particles on its inner surface, and wherein carrier material does not have metallic particles in fact.Metallic particles is carried by zeolitic material and zeolitic material is carried by porous carrier, so this is a two carrier system.At first, require great effort very much in this preparation, secondly, the manufacturing cost of this system is more expensive, because need other member and other method step.
Therefore, target of the present invention is to provide metallic catalyst, the rhodium catalyst that especially in high temperature is used, uses, and it represents quite low heat ageing trend thereby during the long life, keeps its catalytic activity almost constant.In addition, the simple and cost efficient of its preparation.
This target realizes that by the catalysis constituent that comprises porous carrier materials and rhodium wherein rhodium is arranged in the hole of porous carrier materials in fact.
This target is also realized by the method that is used to prepare the catalysis constituent that is described below, comprises step:
A) with sulfurous acid rhodium impregnating porous carrier solution material;
B) porous carrier materials behind the calcining dipping.
Find surprisingly; After at high temperature using, the catalysis constituent that comprises porous carrier materials and rhodium keep its catalytic activity almost constant; Wherein rhodium is arranged in the hole of porous carrier materials in fact, and respective carrier metallic catalyst known in the art is usually because the metallic particles sintering has lost the activity of a great deal of.Catalysis constituent according to the present invention has the heat endurance of obvious increase compared to carrier metal catalyst known in the art.
Especially, high temperature represents pointed advantage in using according to catalysis constituent of the present invention; And corresponding conventional carriers metallic catalyst is tending towards heat ageing faster therein, assembles the bigger unit of formation thereby this is because of leading high temperature causes the high mobility of metallic particles and uniting of particle.For example this is in the situation of exhaust-gas treatment, particularly three-way catalyst (TWC).
In an embodiment of the present invention, the porous carrier materials of pointing out above preferred is the open-pored carrier material.The open-pored carrier material is preferably inorganic open-pored carrier material.
Further the preferred aperture carrier material is to have carrier material unimodal or the multimodal pore size distribution.
According to another embodiment of the present invention, the carrier material of pointing out above preferably includes the material that is selected from down group: titanium oxide, γ-, θ-or Δ-aluminum oxide; Cerium oxide, Si oxide, zinc oxide; Magnesium oxide; Sieve and silica-sesquioxide, silicon carbide, and magnesium silicate or two or more above the mixtures of material pointed out.In addition, preferred carrier materials is made up of one of top material of pointing out or its mixture.
According to another embodiment of the present invention, the carrier material of pointing out above preferred is a zeolitic material.
In this manual; According to (the D.S.Coombs etc. of International Mineralogical Association (International Mineralogical Association); Can.Mineralogist, 35,1997; 1571) definition, zeolitic material mean the crystalline material with the structure that is characterized by the tetrahedron framework that connects together.Each tetrahedron is made up of four oxygen atoms that surround central atom, and wherein this framework comprises the open cavity of passage and cage type formula, and it is taken by hydrone and frequent tradable framework outer cationic usually.The passage of material is enough greatly to enable to use foreign compound.In hydrous material, dehydration mainly is being lower than generation and reversible mostly under about 400 ℃ temperature.
The zeolitic material that comprises in the catalysis constituent can be that zeolite also can be and the zeolite materials similar, silicate for example, aluminosilicate; Aluminate or phosphate, silicoaluminophosphate, metallic aluminium phosphate; The metallic aluminium phosphosilicate, gallium aluminosilicate, gallium silicate; Boroaluminosilicate, borosilicate or titan silicate, wherein preferred especially aluminosilicate and titan silicate.
According to the definition of International Mineralogical Association (D.S.Coombs etc., Can.Mineralogist, 35,1997,1571), term " aluminosilicate " means has formula M N+[(AlO 2) x(SiO 2) y] H 2The crystalline material of the spacial framework of O, it is by SiO 4/2And AlO 4/2Tetrahedron is formed, and connects the three-dimensional network with formation rule through common oxygen atom.According to so-called " Rule ", the atomic ratio of Si/Al=y/x is always more than or equal to 1, and this stops two adjacent electronegative AlO 4/2Tetrahedron occurs each other in succession.Although more exchange point can be used for metal under low Si/Al atomic ratio, the zeolite thermally labile more that becomes gradually.
In this manual, the zeolitic material of pointing out above can the alkali form uses like Na and/or K form, and can the alkaline earth form, ammonium form or the use of H form.In addition, zeolitic material also possibly represented mixed form, like alkali/alkaline earth mixed form.
Zeolite preferably has from 5 to 300 SiO 2/ Al 2O 3Modulus, 10-200 is better, and 15-100 is best.
Zeolitic material preferably can be corresponding to one of following structure type: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST; ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF; CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EON, EPI, ERI, ESV, ETR; EUO, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, IHW, ISV, ITE, ITH, ITW, IWR; IWV, IWW, JBW, KFI, LAU, LEV, LIO, LIT, LOS, LOV, LTA, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER; MFI, MFS, MON, MOR, MOZ, MSE, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NES, NON, NPO, NSI, OBW; OFF, OSI, OSO, OWE, PAR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS; SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN, SFO, SGT, SIV, SOD, SOS, SSY, STF, STI, STT; SZR, TER, THO, TON, TSC, TUN, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YUG and ZON, the wherein zeolitic material of preferred especially β (BEA) structure type.The name that top trigram code term provides corresponding to " IUPAC zeolite NK " (IUPAC Commission of Zeolite Nomenclature).
According to the present invention, the also preferred zeolitic material that uses the amphiphilic compound preparation.The preferred example of previous materials is at US 5,250, points out in 282 and combination is in the present invention by reference.In addition; The suitable zeolitic material of preferred the type is also at " Review of Ordered Mesoporous Materials ", O.Ciesla and F.Schoth, Microporous and Mesoporous Materials according to the present invention; 27; (1999), describe among the 131-49, it also makes up in the present invention by reference.
According to the present invention, the mesopore zeolite material of equal preferred zeolitic material for processing by silicate or aluminosilicate, it closes in document and is called M41S, for example MCM-41, MCM-48 and MCM-50.These zeolitic materials are at US 5,098,684 with US 5,102,643 in describe in detail, it makes up in the present invention by reference.The mesoporous silicate that is called MCM-41 and MCM-48 is the preferably subclass of this family of the present invention.Especially preferred MCM-41, it has the hexagonal array of the mesopore of identical size.The MCM-41 zeolitic material has preferred SiO more than 100 2/ Al 2O 3Mol ratio, better more than 200, best more than 300.Another preferred zeolite material that can in framework of the present invention, use is called MCM-1 for those, MCM-2, MCM-3, MCM-4, MCM-5; MCM-9, MCM-10, MCM-14, MCM-22, MCM-35; MCM-37, MCM-49, MCM-58, MCM-61, the zeolitic material of MCM-65 or MCM-68.
Zeolitic material with ITQ-33 is another suitable zeolitic material.
According to the present invention, rhodium is arranged in the hole of zeolitic material in fact, thereby is arranged in inner surface.In the present invention, " in fact " preferably means the hole (inner surface) that at least 90% rhodium is arranged in zeolite, and at least 95% is better, and at least 99% is good especially, and at least 99.9% is best.Aforementioned ratio is the wt.-% with respect to the gross weight of the rhodium in the catalysis constituent.The rhodium that is not arranged in the inner surface of porous carrier materials exists usually in the following manner: its quantity is lower than detectable limit, or it is to the not influence of the preferred constituent character of the present invention.
Reflect according to zeolite of the present invention or with zeolite materials similar no Rh in X-ray diffractogram (XRD).This shows that rhodium is arranged in the hole of zeolite and on outer surface, does not have bigger bunch (> 5nm).This also can prove (poisoning after lip-deep Rh bunch in selectivity) through CO absorption in FTIR.Catalysis constituent according to the present invention has the Rh-C=O stretching vibration.Even after poisoning, still have the Rh-C=O stretching vibration with the adamantane nitrile.The adamantane nitrile is the molecule of spatial arrangements effort, because its size, it can not pass the hole system of porous carrier.Therefore, as the result of absorption adamantane nitrile, have only Rh bunch (if existence) on the outer surface of porous carrier, to poison.If CO absorption after this is poisoned, this only can retrain Rh bunch of the interior not poisoning of porous carrier materials.After poisoning, still exist the Rh-C=O stretching vibration to show that Rh is arranged in the hole of porous carrier materials with the adamantane nitrile.The intensity that after poisoning, stays is higher than the comparison catalyst in fact.
According to the present invention, " inner surface " means the endoporus system of zeolite, and it means hole/passage on the one hand, means cavity on the other hand.
In an embodiment, the carrier material of pointing out above has the multimodal pore size distribution, and promptly zeolitic material comprises micropore, mesopore and macropore.Reach in this respect in the framework of the present invention, micropore, mesopore and macropore mean the diameter of the diameter that has respectively less than 1nm, 1-50nm, and greater than the hole of the diameter of 50nm.
Preferably comprise the rhodium of 1wt.-% at least according to zeolite of the present invention, 1.5wt.-% is better at least, and 2wt.-% is good especially, 2.5wt.-% or above best, and 3wt.-% especially at least is all for the gross weight of rhodium and carrier material.
For avoiding zeolitic material rhodium overload; This can cause the hole of zeolitic material and channel system to be closed, and follows the accessibility of the catalytic activity rhodium particle of the educt that is used for transforming to reduce, according to another preferred embodiment of catalysis constituent of the present invention; Rhodium ratio in the laden zeolitic material is preferred≤10wt.-%; ≤8wt.-% is good especially, and≤7wt.-% is better, and≤5wt.-% is best.
In principle, be favourable if the rhodium that exists with the rhodium particle form in the zeolitic material (being also referred to as rhodium disperses) has as far as possible little granular size, because the rhodium particle has very high decentralization like this.Decentralization means the ratio between the total quantity of quantity and the rhodium atom in the rhodium particle of the rhodium atom that forms the rhodium particle surface.Yet favourable average rhodium particle diameter also depends on the application that will use the catalysis constituent and the pore size distribution especially pore radius and the channel radius of zeolitic material.According to the preferred embodiment of catalysis constituent of the present invention, the rhodium particle has less than the bore dia of carrier material and greater than the average diameter of channel diameter.Thereby the rhodium particle is mechanically cut in carrier material, and this causes the high resistance to heat aging of catalyst according to the invention.According to the preferred embodiment of catalysis constituent of the present invention, the rhodium particle has the average particulate diameter between the 0.5-5nm, preferred 0.5-4nm, and 0.5-3nm is good especially, and 0.5-2nm is best.Average particulate diameter is preferably confirmed through the decomposition of zeolitic material and by means of the remaining Rh particle of transmission electron microscope (TEM) measurement.
Generally speaking, preferred high as far as possible dispersion value because in this case, metallic atom as much as possible can be free near and be used for catalytic reaction.This means that the high dispersive value of given carrier metal catalyst can use the metal of relative a small amount of to obtain same catalytic activity.
According to another embodiment of catalysis constituent of the present invention, the rhodium particle be separated into 1-10%, preferred more than 20%, good especially more than 30%, the sea is preferred more than 35%, better more than 40%, also preferred more than 45%, the best more than 50%.Dispersion value is confirmed by means of hydrogen according to DIN 66136-2.
In addition, according to another embodiment of catalysis constituent of the present invention, the porous carrier materials especially BET surface area of zeolitic material is preferably 100m 2/ g-1500m 2/ g, 150m 2/ g-1000m 2/ g is better, 200m 2/ g-600m 2/ g is best.The BET surface area will be confirmed through nitrogen absorption according to DIN 66132.
In addition, according to another embodiment of catalysis constituent of the present invention, the catalysis constituent has the sulfur content less than 0.004wt.-%, preferably less than 0.003wt.-%, for the weight of rhodium and carrier material.Low sulfur content is especially favourable, because sulphur is as catalyst poison, especially for noble metal.
Catalysis constituent of the present invention is that compared to another advantage of prior art noble metal (rhodium) only is applied on the member, i.e. porous carrier or preferred zeolite, and as storage place, there is not other carrier material in it simultaneously in the catalysis constituent.Catalyst according to prior art is made up of catalytic activity member (being generally the noble metal on the oxidation carrier) and pure storage member (being generally zeolite).
According to constituent of the present invention thereby be catalyst be again storage hydrocarbon thing.Along with the zeolite ratio increases, the hydrocarbon storage volume also obviously increases (for example referring to EP 691 883 B1, US 5,804,155).If for example the three-way catalyst waste gas that do not reach essential operating temperature and formation as yet still can not oxidation or reduction, the storage volume particular importance.In addition, can practice thrift preparation process thereby also practice thrift cost.
Therefore, of the present invention theming as, wherein have only a carrier material to be present in the catalysis constituent according to catalysis constituent of the present invention.The catalysis constituent does not preferably have other carrier material.Thereby it is single carrier system.
According to embodiment, the catalysis constituent by or form by porous carrier materials and rhodium in fact, porous carrier materials preferred zeolite material, wherein rhodium is arranged in the hole of porous carrier materials in fact and has only a carrier material to be present in the catalysis constituent.
In the present invention, " in fact by ... form " mean and can have other member, itself or be positioned under the detectable limit or to the not influence of the preferred constituent character of the present invention.
Of the present invention another themes as the preparation method of aforesaid catalysis constituent, comprises step:
A) with sulfurous acid rhodium impregnating porous carrier solution material;
B) porous carrier materials behind the calcining dipping.
According to the present invention, porous carrier materials this also preferred zeolite or with the zeolite materials similar, as stated.Thereby same parameter is selected to be applied to according to the method for the invention.
According to a further embodiment of the method according to the invention, between the step a) of the inventive method and step b), drying steps is arranged.
Drying steps carries out between dipping and calcining.Baking temperature is between 25 ℃ and 250 ℃, and is better between 100 ℃ and 180 ℃ between preferred 50 ℃ and 200 ℃, especially preferred 120 ℃.
Drying was preferably carried out more than 1 minute, and is better more than 1 hour, good especially more than 5 hours, best more than 12 hours, wherein first-selected 10 hours drying time.In this connection, be favourable if the duration of drying steps is no more than 48 hours, preferably be no more than 24 hours.
Calcining is preferably carried out in air, thereby in containing the oxygen atmosphere, carries out.Term " calcining " means the high temperature that is heated on the material or changes handled material or its formation on the structure usually.For example can realize thermal decomposition, phase transformation or remove volatile substance through calcining.
The calcining of the porous carrier materials behind the dipping is preferably carried out under the temperature between 300 ℃-1200 ℃, and 400 ℃-950 ℃ are better, and 500 ℃-900 ℃ are outstanding good, the temperature between also preferred 550 ℃-850 ℃, and 650 ℃-830 ℃ are better, 750 ℃ of-780 ℃ of the bests.
In addition, preferred especially calcining is carried out under at least 770 ℃ temperature, preferred 800 ℃ or more than.During at least 770 ℃ temperature lower calcination,, can obtain not have to a great extent the catalysis constituent of sulphur by means of the inventive method although load for example 3wt.-% with respect to the high rhodium of the weight of rhodium and porous carrier materials.Therefore; By means of the inventive method, for example can produce the rhodium that comprises 1-5wt.-% (with respect to the weight of rhodium and porous carrier materials) and have less than 0.004wt.-% preferably less than the catalysis constituent of the sulfur content of 0.003wt.-% (with respect to the weight of rhodium and carrier material).Low sulfur content is especially favourable, because sulphur is as catalyst poison, especially for noble metal.Low sulfur content is unexpected, especially when preparation catalysis constituent, has used sulfur-bearing initial compounds (sulfurous acid rhodium).
The rate of heat addition during the calcining is preferably 0.5 ℃/min-5 ℃/min, 1 ℃/min-4 ℃/min is better, and 2 ℃/min is best.
The calcining duration under maximum temperature, 30 minutes to 12 hours better preferably in 1 minute to 48 hours scope, and 1 hour to 7 hours good especially, wherein the calcining duration of first-selected 5 hours or 6 hours.
As the result of calcining, rhodium (precursor) compound forms, and if necessary, it preferably can reduction after calcining.Yet in principle, reduction also can take place during calcining, yet wherein must use reduction atmosphere rather than air.
Another embodiment according to the inventive method is selected from Ni, Sn, Ag, Mn, Pb, Co, Fe, Cr, at least one additional metals of Ce and Cu preferably before step a), during or introduce afterwards in the porous carrier materials, preferably with the form of oxide.Preferably, this metal is selected from Ni, Mn, and Co, Fe, Cr, Ce or Cu especially are preferably selected from Ni, Fe, Ce and/or Cu.
The oxide of the preferred metal of pointing out above the introducing in the method according to the invention is because the catalytic activity Rh kind of such oxide in the catalyst that can obtain according to the present invention provides other heat endurance.
In the catalysis constituent that is obtained in the scope of ratio at 0.1-10wt.-% of metal oxide, preferred 1 – 5wt.-%, especially preferred 1.5-3wt.-% is all for the weight of the catalysis constituent that after calcining, obtains.
Metal oxide being introduced in the catalysis constituent that obtains according to the present invention can be before with sulfurous acid rhodium impregnating porous carrier solution material, carry out simultaneously afterwards or with it.If this carries out before or after being introduced in dipping, preferably carry out by means of ion-exchange (liquid or solid exchange) in the known manner.If this takes place before being introduced in the dipping rhodium, preferably the porous carrier materials with metal exchange is flooding rhodium calcining before, and wherein aforementioned metal is converted into oxidised form.If this introducing is carried out with dipping simultaneously, produce the corresponding mixed solution of required component (sulfurous acid rhodium, not necessarily, slaine), and flood porous carrier with this mixed solution and calcine then.
The reduction that can after calcining, carry out preferably uses the reducing gas (hydrogen, hydrocarbon, carbon monoxide, ethene, methyl alcohol, ethanol etc.) or the mixture of inert gas to carry out.Preferred inert gas for example is argon, helium, neon etc.Inert gas will be regarded carrier gas as in reduction step, and wherein hydrogen or another reducing gas are preferably the concentration of 1-10vol.-%, and 3-7vol.-% is better, and about 5vol.-% is good especially, all for the cumulative volume of reducing gas and inert gas.
Till reduction proceeds to the rhodium precursor compound usually fully or almost completely (preferred more than 95%) transforms.Reduction is preferred to be carried out 3-7 hour, and 4-6 hour better, and about 5 hours good especially.
Reduction is preferably carried out under the temperature that increases.Reduction preferably is carried out under 200-500 ℃ temperature, and 250-350 ℃ is better, about 300 ℃ outstanding good.For this reduction, catalyst is placed in the catalyst bed usually and reducing agent flows through catalyst.Equally, catalyst can cover with reducing gas, and advantageously, reaches the temperature of increase.The increase of temperature for example can be carried out through the heatable catalyst bed.Equally, also possibly heat in advance by reducing gas, for example through the heated air inlet pipe, wherein the reducing gas after the heating conducts above the catalyst that will reduce.
Can carry out through immersing dipping, spraying dipping or incipient wetness method with sulfurous acid rhodium solution impregnation zeolite.Dipping preferably carries out through incipient wetness method.
Find surprisingly; Through at high temperature in air, calcining then with the just wet dipping porous carrier materials of sulfurous acid rhodium solution preferred zeolite powder; Can make the catalysis constituent, even after this high temperature load, wherein most of rhodium still is retained in the hole or zeolite pore of porous carrier materials.This can prove through X-ray diffractogram (XRD) in FTIR, also can after poisoning with adamantane nitrile selectivity, prove through CO absorption.XRD and FTIR are the standard chemical analytical method.Suppose the XRD spectrum of catalysis constituent thereby do not have the Rh signal, but because the outer surface of porous carrier materials does not have or do not have fully the Rh particle of diffraction according to the X-ray radiation size of rhodium diffraction pattern, about usually 5nm in fact.
Find equally surprisingly, thereby the catalysis constituent that makes is compared the anti-sulphur property that known system has increase.Catalytic activity according to the constituent of heat ageing of the present invention is not poisoned change by sulphur, is high temperature desulfurizing after sulphur poisons.
The catalysis constituent that makes according to the present invention represents the ageing properties of improvement equally.
The catalysis constituent that makes according to the present invention is that compared to another advantage of prior art noble metal only is applied on the member, i.e. porous carrier or zeolite, and it is simultaneously as storage place.
According to constituent of the present invention thereby be catalyst be again storage hydrocarbon thing.
Catalyst according to prior art is made up of catalytic activity member (being generally the noble metal on the oxidation carrier) and pure storage member (being generally zeolite).Thereby can practice thrift preparation process thereby also practice thrift cost.
The catalysis constituent that makes according to the present invention is that compared to another advantage of prior art noble metal only is applied on the member, i.e. porous carrier or zeolite, and it is simultaneously as storage place.Catalyst according to prior art is made up of catalytic activity member (being generally the noble metal on the oxidation carrier) and pure storage member (being generally zeolite).
According to constituent of the present invention thereby be catalyst be again storage hydrocarbon thing.Along with the zeolite ratio increases, the hydrocarbon storage volume also obviously increases (for example referring to EP 691 883 B1, US 5,804,155).If for example the three-way catalyst waste gas that do not reach essential operating temperature and formation as yet still can not oxidation or reduction, the storage volume particular importance.In addition, can practice thrift preparation process thereby also practice thrift cost.
Therefore, theme of the present invention still especially uses the catalysis constituent of prepared in accordance with the method for the present invention.
Another theme of the present invention is being used as reducing catalyst and storage hydrocarbon thing as stated or according to the catalysis constituent that said method makes.Zeolite is known as storage hydrocarbon thing.Yet, disperse to combine with high rhodium in the zeolite pore, to store up the reducing catalyst of hydrocarbon thing function equally very suitable as having corresponding accumulation.Because rhodium only is applied on the zeolite, and be applied on other metal oxide, cause the simple antigravity system that can favorable cost produces unlike that kind in the prior art.
Advantageously, the catalysis constituent is as the member of three-way catalyst.There, it mainly helps nitrogen oxides reduction NO xAnd as storage hydrocarbon thing.Owing in catalysis constituent according to the present invention, comprise active component Rh, also can increase about the selectivity of hope product.Thereby theme of the present invention still is, and catalysis constituent according to the present invention is used for the chemical catalysis effect.
Another theme of the present invention is that the catalysis constituent is used in the catalyst structure.Catalyst structure comprises catalyst carrier, and wherein the catalysis constituent appears on the catalyst carrier as coating.
The invention still further relates to catalysis constituent according to the present invention and be used in the catalytic action processing, can occur the temperature more than 700 ℃ when wherein having at least.
According to the embodiment of purposes of the present invention, the catalytic action of pointing out is above handled to be preferably and is removed the waste gas that forms during biology or the combustion of fossil fuel, like industry or vehicles waste gas, and preferred automobile, steamer, locomotive engine waste gas etc.
Advantageously, catalysis constituent according to the present invention can be treated to washcoated layer, thereby is applied on the catalyst mouldings.Those skilled in the art will know that and how to prepare so washcoated layer.The paint-on technique of necessity that is used for the coated catalysts formed body is well-known to those skilled in the art.Therefore, for example behind the dipping and dried zeolite treatment be that water applies dispersion liquid.Adhesive such as Ludox can add in this dispersion liquid.The viscosity of dispersion liquid can be set through proper additive, therefore maybe be in single job step the coating of necessary amount be applied on the flow path wall.If this is impossible, then apply and can repeat several times, wherein each coating that newly applies if necessary, is calcined through middle dry fixing.The parameter of pointing out above selects to be applied to drying and the calcining heat at this.
Another theme of the present invention thereby for comprising washcoated layer according to catalysis constituent of the present invention.
According to another embodiment, catalysis constituent according to the present invention is preferably formed and is powder, formed body or monolithic.Preferred formed body for example is ball, ring, cylinder, hole cylinder body, trilobal or cone, and preferred monolithic is a honeycomb ceramics.
Of the present invention another themes as the catalyst structure that comprises aforesaid catalysis constituent.The other parameter of pointing out is as follows selected to be applied to equally according to the purposes of catalysis constituent of the present invention in catalyst structure.
Catalyst structure comprises catalyst carrier, and wherein the catalysis constituent appears on the catalyst carrier as coating.
Metal or ceramic monolith, nonwoven or metal foam useful as catalysts carrier or carrier formed body.According to the present invention, other catalyst mouldings known in the art or catalyst carrier also are fit to.Especially preferably the metal or the ceramic monolith that have a plurality of parallel channels opening, these access portal have washcoated layer.Catalyst carrier preferably has the access portal of circle, triangle, square or polygonal cross-section.
Metallic honeycomb bodies is formed by sheet metal or metal forming usually.For example honeycomb ceramics produces through alternately arranging sandwich construction sheet or paper tinsel.Preferably, these arrangements alternately are made up of one deck smooth sheet and corrugated plate, and wherein ripple for example can form sinusoidal waveform, trapezoidal, Ω shape or zigzag.Proper metal honeycomb ceramics and preparation method thereof is for example described in EP 0 049 489 A1 or DE 28 56 030 A1.
In the catalyst carrier field, metallic honeycomb bodies has the advantage of faster heating, thereby under cold start, represents better reactivity worth usually based on the catalyst carrier of metal substrate.
Honeycomb ceramics preferably has the cellular densities of 30-1500cpsi, and 200-600cpsi is better, and about 400cpsi is good especially.
The catalyst mouldings that catalysis constituent according to the present invention can apply on it can be formed and can be through extrusion molding or through reeling, pile up or the folded metal paper tinsel making by any metal or metal alloy.In the waste scavenging field, known have a heatproof alloy that key component is iron, chromium and aluminium.For catalysis constituent according to the present invention; The monolith catalyst carrier that preferably can freely be flow through; Have or be not used in stir waste gas or metal foam interior leading edge all can, it has big internal surface area and catalyst according to the invention very well adheres on it.Yet, also can use the catalyst carrier that in metal forming, has slit, hole, perforation and impression.
Equally, can use the catalyst carrier of processing by ceramic material.Preferably, ceramic material is the inert material with little surface area, like cordierite, mullite, aluminium titanate or alpha-aluminum oxide.Yet employed catalyst carrier also can be made up of the carrier material with high surface area, like γ-aluminum oxide.
Metal foam is also useful as catalysts carrier of metallic open cell foam material for example.In framework of the present invention; Term " metallic open cell foam material " means the foamed material of being processed by any metal or any alloy; It can not necessarily also comprise additive and have a plurality ofly through pipeline hole connected to one another, so gas can be through the foamed material conduction.
Because hole and cavity, the metallic open cell foam material has low-down density, but has considerable rigidity and intensity.The generation of metal foam is for example carried out by means of metal dust and metal hydride.Two kinds of powder mix usually to compress through hot forming or extrusion molding then and are moulding material.Afterwards, moulding material is heated to above the temperature of melting point metal.Metal hydride release hydrogen and mixture form.
Yet, produce other possibility of metal foam in addition, for example through gas is blown into metal bath, this melt before was caught and can spumes through adding solid constituent.For aluminium alloy,, add silicon carbide or the aluminum oxide of 10-20vol.-% for stable.In addition, having 10ppi can be through special precision casting technology generation to the open cell metallic foam structure in about 50ppi aperture.
In principle, but also extrusion molding and injection molding form catalyst carrier.At this, metal and/or ceramic material are possible, wherein under the situation of ceramic material, add molded annex and bond and other additives.The carrier of extrusion molding can adopt any geometry, the structure of pointing out above preferred.
The catalyst according to the invention member preferably includes two-layer at least, and the ground floor of wherein distributing to catalyst carrier comprises oxidation catalytic activity member and storage oxygen member, and the second layer comprises aforesaid catalysis constituent.
Ground floor preferably includes platinum and/or the palladium on the oxidation carrier material, the especially preferred Al of oxidation carrier material 2O 3Cerium oxide or cerium/Zirconium oxide are preferably used as storage oxygen member.Al 2O 3With the mol ratio of cerium oxide or cerium/Zirconium oxide can be according to application change and preferred in the scope of 70:30-30:70.In addition, Ce/Zr can be according to application change and preferred in the scope of 0.1:9.9-9.9:0.1 than also.
Pt on the carrier (like honeycomb) after advantageously selecting the concentration of platinum and/or palladium make to apply and/or the concentration of Pd are 0.5-5g/l, preferred 0.6-3g/l, and the 1g/l carrier bulk is good especially.Platinum also can all be replaced by palladium.
The upper strata thereby the second layer comprise according to catalysis constituent of the present invention.Employed amount meets desirable Rh concentration.The Rh concentration of preferred 0.05-1g/l carrier bulk (like the honeycomb volume), about 0.1g/l is good especially.Since very high according to the Rh concentration in the catalysis constituent of the present invention, at 3wt.-%, compare known catalyst at present, need the obviously little catalysis constituent that gets most amounts.Thereby possibly economize on resources and can reduce the layer thickness on the carrier, thereby also fall the pressure in the catalyst according to the invention member.
In theory, the catalysis constituent quantity of saving can be offseted by other member, for example stores up the quantity of oxygen member as storage hydrocarbon thing or increase through the zeolite member of other quantity.
The present invention will combine some embodiment to be described in detail now, but these embodiment are not regarded as limiting scope of the present invention.In addition, with reference to following accompanying drawing.
Fig. 1 shows two H-BEA zeolites that load Rh and calcines XRD spectrum afterwards in air or under the argon atmosphere.
Fig. 2 shows the CO conversion ratio that three-way catalyst according to the present invention is compared traditional catalyst.
Fig. 3 shows the propylene conversion that three-way catalyst according to the present invention is compared traditional catalyst.
Fig. 4 shows the NO conversion ratio that three-way catalyst according to the present invention is compared traditional catalyst.
Embodiment
Example 1
Dry carrier (H-BEA-35) is from the rhodium of sulfurous acid rhodium solution impregnation 3wt.-% and 120 ℃ of following dry nights (8 hours).Zeolite behind the dipping is calcined down at least 770 ℃ (800 ℃ of ≈) in air then.The rate of heat addition is 2 ℃/min, and gas volume is 2l/min.
Example 2
For relatively, produce same sample, but under the argon atmosphere, calcine.
XRD spectrum (referring to Fig. 1) shows, does not reflect when calcining has Rh when in air, carrying out, and after calcining under the argon atmosphere, can see tangible Rh reflection.Do not have the Rh signal indicating, although high calcining heat, the rhodium that does not have bigger bunch formation to reach high degree of dispersion from the teeth outwards is arranged in the passage/hole of zeolite.In addition, after calcining, catalyst comprises sulphur hardly, and (the calcining back is less than 0.003wt.-% in air; The calcining back is less than 0.014wt.-% under the argon atmosphere).
Example 3: coating and performance are relatively
Example 3.1: compare test
For comparing with composition according to the present invention, the standard method that the Zirconium oxide basis is used to produce rhodium catalyst is with Rh (NO 3) 3Dipping is also calcined down at 550 ℃ in air.Rhodium concentration also is 3wt.-%.
Example 3.2: apply
Make the Rh zeolite of 16.6g reach Rh-ZrO with the Ultra-Turrax agitator from example 3.1 from example 1 and 2 2Be suspended in respectively and have 5.9g SiO 2In the 150ml water of adhesive and 37.3g Zirconium oxide.Suspension is worn into the d of about 2 μ m with the planetary ball mill (Retsch PM100) of 10mm ball with the stable Zr oxide of yttrium 50Granular size.Under each situation, cordierite honeycomb (400cpsi) is coated this washcoated layer and calcining, and therefore 0.3g Rh/l honeycomb volume is included on the honeycomb when finishing.
Example 3.3: performance relatively
CO and propylene oxidation and NO reduction from washcoated layer of catalyst monolith that produces of example 1,2 and 3.1 are used in test in reactor under following condition.
Space velocity 70000h -1
CO 1.5vol.-%
C 3H 6 110ppm
NO x 2000ppm
O 2 1vol.-%
CO 2 10vol.-%
H 2O 10vol.-%
T?var 5K/min
Test condition is near λ=1 [actual ~ 1.3]
After this test, these honeycombs are 900 ℃ of aging 1 hour and tests once more under specified criteria down.
Use these results, can obviously find out from Fig. 2-4, at fresh state (solid line), the rhodium on the zeolite (curve with rhombus) has high activity, ZrO 2On rhodium (having leg-of-mutton curve) have lowest activity.Under each situation, catalyst according to the invention (square) is in the centre.Yet the advantage of catalyst according to the invention (dot-dash curve) after aging becomes clearly.The heat endurance of catalyst according to the invention is far above two comparative example, and the catalytic activity of two comparative example stress influence of being heated is much better than.

Claims (17)

1. a catalysis constituent comprises porous carrier materials and rhodium, it is characterized in that, said rhodium is arranged in the hole of said porous carrier materials in fact.
2. according to the catalysis constituent of claim 1, it is characterized in that, said porous carrier materials be zeolitic material or with the zeolite materials similar.
3. according to the catalysis constituent of claim 2, it is characterized in that said zeolitic material is the zeolitic material of beta structure type.
4. according to the catalysis constituent of claim 2, it is characterized in that said zeolitic material is the zeolitic material of MCM structural group.
5. according to the arbitrary described catalysis constituent of claim 1-4, it is characterized in that, comprise the rhodium of 1.5wt.-% at least, preferably 3wt.-% at least.
6. according to the arbitrary described catalysis constituent of claim 1-5, it is characterized in that the XRD spectrum of said catalysis constituent does not have the rhodium signal.
7. according to the arbitrary described catalysis constituent of claim 1-6, it is characterized in that with respect to the weight of rhodium and carrier material, said catalysis constituent has the sulfur content less than 0.004wt.-%.
8. according to the arbitrary described catalysis constituent of claim 1-7, it is characterized in that having only a carrier material to be present in the said catalysis constituent, and said catalysis constituent there is not other carrier material.
9. be used to prepare method, comprise step according to the arbitrary described catalysis constituent of claim 1-8:
A) with sulfurous acid rhodium impregnating porous carrier solution;
B) porous carrier behind the calcining dipping.
10. according to the method for claim 9, wherein said calcining is carried out in air.
11. according to the method for claim 9 or 10, wherein said calcining is carried out under 500-900 ℃ temperature.
12., wherein after said calcining, reduce according to the arbitrary described method of claim 9-11.
13. according to the purposes of the arbitrary catalysis constituent described or that obtain according to the arbitrary described method of claim 9-12 of claim 1-8, as reducing catalyst and storage hydrocarbon thing.
14. the purposes according to claim 13 is characterized in that, said catalysis constituent is the member of three-way catalyst.
15. a catalyst structure comprises according to the arbitrary described catalysis constituent of claim 1-8 or comprises the catalysis constituent that makes according to the arbitrary described method of claim 9-12
16. the catalyst structure according to claim 15 comprises carrier, wherein said catalysis constituent appears on the said carrier as coating.
17. according to the catalyst structure of claim 15 or 16, comprise two-layerly at least, the ground floor of wherein distributing to said carrier comprises oxidation catalytic activity member and storage oxygen member, and the second layer comprises arbitrary described catalysis constituent according to claim 1-8.
CN201080052490XA 2009-11-18 2010-11-16 Age-resistant Rh-zeolite catalyst Pending CN102665905A (en)

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