CN1004992B - 制备稀土金属复合氧化物/合金蜂窝体催化剂的方法 - Google Patents
制备稀土金属复合氧化物/合金蜂窝体催化剂的方法 Download PDFInfo
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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
- 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
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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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
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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
- 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
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/524—Spinel
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
合金蜂窝载体的稀土催化剂是用于工业废气净化、汽车排气和空气净化的。本发明的特点在于:它的载体是多孔、双面有金属毛刺的、耐高温的、高电阻的含铝合金带做成的薄壁蜂窝体。它的催化活性物是ABO3晶型或K2MgF4晶型的非贵金属复合氧化物,其主要成份是轻混合稀土和铁。它的载附方法是多种金属元素严格按化学计量比例的快速涂布干燥法。它具有强度大、导热性好、处理能力大、价格较廉,能抗铅等优点。
Description
合金蜂窝载体的稀土催化剂是用于工业废气净化、汽车排气净化和空气净化的。它通过氧化或还原反应将有害的废气转化为二氧化碳和水,同时放出反应热,其反应式如下:
国内外现有的合金蜂窝载体催化剂都是用贵金属作催化活性物质,以一般的含铝炭素钢或不锈钢薄带为基材的;现有的稀土催化剂则或是做成无载体的、或是以三氧化二铝等颗粒,或是用陶瓷蜂窝作载体的,其催化活性物质用的是ABO3晶型或K2MgF4晶型等金属复合氧化物,其主要成份是镧系金属、碱土金属和钴、镍、铜、锰等变价金属。本发明则是由稀土复合氧化物和合金蜂窝载体二者牢固结合而成,是一种新型的组合催化剂。
一、载体
本发明的载体是一般的耐高温、高电阻的铁铬铝或镍铬铝带材,与
Cat.表示催化剂
t.表示温度
其他合金蜂窝载体不同之处在于,要把它轧制成0.07~0.08mm厚、50mm(或25mm或30mm)宽的长带,再在双面轧出0.4×0.4mm的小孔(孔距1.1~1.2mm),双面孔边都有金属毛刺的突出物,其中大部份带子要再经过波纹机轧出波纹(波高1.1~1.7mm,波距3mm左右)。这些带材还需经过除油、酸蚀粗化和热活化(在650℃~750℃氧化气氛中加热1~2小时)的予处理工序,才能获得表面有γ-AL2O3保护层的活化基材。然后再把一条波纹带和一条平带一起绕卷,即可得到园形或椭圆形蜂窝载体。如果把波纹条和平条间隔排列亦可得到长方形、方形等蜂窝载体,可根据需要而定。附图1即载体加工流程示意图。
本发明的载体与颗粒状的或陶瓷蜂窝载体相比,有如下特点:
1、由于合金的强度大、导热性好,所以本载体的耐震、耐冲击、耐腐蚀、耐大幅度温度波动的性能都明显地优于陶瓷蜂窝载体。
2、由于合金的延展性好,所以本载体的蜂窝孔孔壁很薄,孔道密度和自由截面积就大,因而本催化剂单位体积的处理能力要比陶瓷蜂窝作载体的大一倍。
3、由于合金表面形成了一层以γ-AL2O3为主的氧化物膜,使载体具有了良好的抗高温氧化性,耐腐蚀性好,同时又提高了载体的比表面积。又由于铝是从金属内部迁移到表面的,故不会发生表面氧化膜脱落的现象。
本发明的载体与国内外现有的合金蜂窝载体相比,由于双面带毛刺的小孔增加了载体表面的附着力和比表面积,使催化活性物易于涂上,而且催化活性良好。尤其是合金蜂窝载体表面和催化活性物质之间可以设法形成金属链,使本发明的涂层载附非常牢固。这很有利于延长催化剂的使用寿命。
此外,耐高温、高电阻的载体还可以直接通电加热,所以用本发明方法制成的催化剂做成催化加热元件在通电以后,其表面可以迅速地达到足够的温度以保证催化反应进行,从而可省去废气予热器,节省了催化净化装置的基建投资和运转费用。
二、催化活性物质:
本发明的催化活性物质属于钙钛矿结构(ABO3晶型)或尖晶石结构(K2MgF4晶型),但与一般的稀土催化剂相比,其特点是主要成份是轻混合稀土和铁,优点是原料来源广泛而价格较廉。在上述二种结构中,A位是化学原子序数11-51,56-71或89-103的贱金属阳离子,B位是离子半径0.4~1.4A°的变价金属阳离子。在ABO3结构中A位离子总数应等于B位的离子总数;在A2BO4结构中,A位的离子总数应二倍于B位的离子总数。阳离子A和B的电荷总数均等于氧离子的电荷总数。本发明的特征在于,在ABO3型结构中,A位用轻混合稀土或镧其克原子比是0.6~0.8,锶或钙,其克原子比是0.4~0.2,B位用铁,克原子比是0.5~0.8,锰和/或铜,或/和镍,克原子比是0.5~0.2,也可加入微量钯,克原子比是0.01。在K2MgF4晶型结构中(以A2BO4表示),A位用轻混合稀土和镧,克原子比是1.4~1.8,锶和钙,克原子比是0.6~0.2,B位用铁,克原子比是0.5~0.8,镍,克原子比是0.5~0.2。
本发明中,催化活性物质的代表式是:
〔RE1-xSrx〕〔Fe1-yMny〕O3或
〔La1-xSrx〕〔Fe(1-y-ε)MnyPdε *〕O3
或
式中克原子比X=0.2~0.4 y=0.2~0.5 ε=0.01
X1=0.1~0.3,X2=0.1~0.3,y1=0.2~0.5
*:需降低反应起始温度时,才在B位组分中加入极微量的钯。
由于本发明的催化活性物质是多种金属复合氧化物,比较疏松;载体基材上又轧有很多均匀小孔,故本催化剂类似于多孔吸声材料。声波入射后,引起材料空隙中空气的振动,并与孔壁产生摩擦,使声能转变为热能,使噪声衰减。当几块催化剂按一定距离间隔放置时,气流通过蜂窝孔后突然扩散,再次进入蜂窝通孔,再次扩散。这正符合微孔扩大消声原理,使合金蜂窝催化剂组对气流噪声起抑制作用,使催化反应器可同时成为消声器。
三、载附方法
催化剂的载附方法,是指催化活性物质载附于载体上的方法。通常采用浸渍法,即把载体浸没在催化活性物质的溶液中,浸渍一段时间后再干燥、焙烧而成。其他还有共沉淀法,化学镀法,喷雾干燥法,电镀法等,也有用冷冻干燥法、混炼法、冶金固结法,离子轰击法等做催化剂的。用上述方法都不能把所需的各种金属元素严格按化学计量定比地载附于金属载体之上。如浸渍法,把合金载体浸在有多种金属离子的镀液里,会发生离子交换反应,各种金属元素的电极电位不同,则进行离子交换反应的能力也不同,于是原有配比被破坏,载附于载体上的大多是那些最易得到电子的金属元素。如果用热喷涂法,则由于各金属元素的溶点、沸点不同、涂层的配比也无法确切掌握。
本发明则是一种能把多组分的催化活性物质严格地按化学计量比例、均匀地、牢固地定比载附于合金蜂窝载体之上的方法,可取名快速涂布干燥法。其工艺流程如附图2所示:活化载体条绕卷于绕轴(1)及(2)〔例如轴(1)绕波纹条,轴(2)绕平条〕;同时卷出,分上、下二层进入快速涂槽(3);带涂液的带子立即进入涂布窑的干燥段(4),再通过盐类分解段(5)和初步氧化段(6),再绕于绕轴(7)和(8)。波纹带和平带可以一起绕,也可分开绕。按需要成型后,将成型块12装入小车13,沿轨道14通过氧化窑的予热段15,氧化段16和冷却段17。推出炉体,催化剂就制备完毕。带材走速1~2米/分,涂布时间0.5~0.6秒。涂布窑干燥段的温度控制在110~200℃,分解段350~450℃,氧化段650~750℃,氧化窑予热段为350~450℃,通过0.5小时;氧化段650~850℃,通过1.5小时;冷却段通过0.5小时。如果一次涂得不匀或不够量,可涂第二次。涂布窑排出的废气可由风机9抽出,经净化装置净化后放空。本方法的特点是:涂液严格按所需化学计量配制,要混合均匀;涂布在室温下进行,速度很快,使金属载体与涂液中的金属离子来不及发生置换反应。这就保证了涂层的化学结构和催化剂的性能。
实施例:
(一)载体加工
买1.0mm厚的铁铬铝OCr21Al6带材,其主要成份为Cr21-24%,Al6.5-7.5%;其他含稀土0.03%,Ti0.15%,CO0.5%,C≤0.06%,Si≤0.06%,Mn≤0.06%,S≤0.03%,P≤0.03%;Fe为余量。最高使用温度1200℃。延伸率≥12%,冷弯90°次数≥5次。比电阻1.4±0.1Ω·mm2/M。
经二辊(1)及四辊(2)冷轧机数次,(退火温度800±20℃)轧成0.07-0.08mm厚。再经轧眼机(3),在双面轧出带毛刺的均匀小孔,小孔0.4×0.4mm,孔距1.2mm,孔穿透率≥90%。再经波纹机(4)轧出波纹,波距3.1mm,波高可调节,在1.1-1.7mm。
铁铬铝带经50℃除油剂除油(7)。水洗(8)后再经38%工业盐酸浸蚀(9)5-8分钟。在超声波清洗器(12)内用无离子水(13)彻底洗净。再经活化炉(14),在650℃至750℃氧化气氛中通过,使表面形成足够量的氧化膜保护层。
(二)催化剂制备
1、称硝酸镧234.84克、硝酸锶63.49克、硝酸铁318.98克、硝酸锰35.79克、硝酸钯2.30克,溶解于水,均匀混合,制得溶液2000毫升,放入快速涂布装置(图2)的涂槽3。此时涂布窑的干燥段温度在110-200℃间,分解段温度在350-450℃间,初步氧化段的温度在700-750℃间。然后启动装置,已经过除油,粗化和活化等处理的铁铬铝波纹带和平带分别自绕轴1和绕轴2同时卷出,分上下二层以1-2米/分的速度通过装置,在绕轴6上,波纹带和平带一起绕卷成蜂窝型园柱体。可得〔La0.7Sr0.3〕〔Fe0.79Mn0.2Pd0.01〕O3的催化剂4~5公斤。大量成型后的催化剂块可装入500×300×150mm3的小车13,每隔10分钟推一车进氧化密进行最终氧化。该窑予热段温度350~450℃,小车在予热段共30分钟。该窑氧化段温度700~750℃,小车在氧化段共90分钟。最后,小车用30分钟通过冷却段,被推出窑外。所得催化剂中,总重的7~8%为催化活性物质。
这种催化剂的适用性及净化效果请见图3、4、5。它同贵金属钯催化剂的性能对比(载体相同)详见图6、7、8。它对空气钢瓶空气的净化效果示于图9。它的空速特性及吸声系数示于表1、2。
表1 空速特性对比
*废气含C3H61%含CO0.2%
表2 催化剂吸声系数
这种催化剂用于漆包机尾气净化,实用寿命已超过4年
2、称轻混合稀土98.0克,加硝酸100毫升,溶解,称硝酸锶84.65克,硝酸铁238.7克,硝酸锰35.79克、硝酸铜37.51克,都溶于水。和制得的硝酸镧溶液均匀混合,得溶液2000毫升,放入快速涂布装置。用同上的方法可制得〔RE0.6Sr0.4〕〔Fe0.59Mn0.2Cu0.2〕O3催化剂约4公斤。
这种催化剂用于汽车排气的净化和消声、效果良好,实际使用寿命已超过5.8万公里。本催化剂的汽车排气净化器(HF型净化器)和原车消声器的对比数据示于表3和表4。
3、称硝酸镧454.90克、硝酸锶63.49克、硝酸钙49.22克、硝酸铁242.27克,硝酸镍73.08克,溶解于水,配制成2500毫升混合溶液,放入快速涂布装置的涂槽。除了涂布窑和氧化窑的温度改为800~850℃以外,其余方法及条件均同例1。所得催化剂〔La1.4Sr0.3Ca0.3〕〔Fe0.6Ni0.4〕O4约5公斤。
这种催化剂用于含氮氧化物的废气治理时,废气空速10000时-1,温度300℃时,100ppmNOx的净化率99.4%。
用以上(例1-例3)方法制得的催化剂可根据用户的要求灵活成形。如净化工业废气用的催化剂可做成250×200×50mm3的长方形或200×200×50mm3的方形块组装成催化剂框,也可做成φ280mm×50mm或φ200mm×30mm的催化加热元件装入工业废气催化净化装置的催化反应筒。当使用于汽车排气净化和消声时,可做成φ100mm×25mm或φ140mm×25mm等园带块,也可做成(φ340+170×170)mm2×25或(φ120+47×47)mm2×25mm的椭园形块。
表3 BJ-492发动机台架试验结果*
*HF型净化器装ABO3型催化剂1.7升,发动机使用含铅汽油
表4 使用HF型汽车节油净化消声器(以乙表示)和原市售消声器(以甲表示)的对比结果
按本发明所制催化剂的一般特性举例于表5
表5 一般特性
本催化剂失效后可以再生。再生试验结果列于表6。试验结果证明,可逆性因素造成的催化活性下降,可以针对原因进行再生。已完全失效的催化剂,可以重复利用其载体,重涂活性组份后,再次投入使用。
表6 催化剂再生试验结果
附图说明
图1 载体加工流程示意图
1 二辊轧机 6 水浴 11、水洗槽
2、四辊轧机 7、除油剂 12、超声波清洗槽
3、轧眼机 8、水洗槽 13、水槽
4、轧波纹机 9、酸蚀槽 14、活化炉
5、绕轴 10、转轴
图2、催化剂制备流程示意图
15、绕轴 22、成型室
16、快速涂槽 23、成型催化剂块
17、涂布窑干燥段 24、小车
18、〃〃〃分解段 25、轧道
19、〃〃〃氧化段 26、氧化窑予热段
20、抽风机 27、〃〃〃氧化段
21、NOx净化器 28、〃〃〃冷却段
图3、图4、图5、ABO3型合金蜂窝催化剂对有机废气的净化曲线进气空速10000h-1,有机物名称及浓度(ppm)如下:
(1)、正己烷9065ppm (2)、异辛烷8565ppm
(3)、环乙烯5279ppm (4)、冰醋酸5232ppm
(5)、甲醛5000ppm (6)、环己酮6855ppm
(7)、乙醇5475ppm (8)、正丁醇10000ppm
(9)、醋酸乙酯4870ppm (10)、苯10000ppm
(11)、甲苯酚5807ppm (12)、吡啶600ppm
(13)、乙腈6011ppm (14)、氧化碳9200ppm
图6、催化活性对比图
A、本发明ABO3型催化剂 B、0.5%钯催化剂
废气含丙烯10000ppm,废气空速10000h-1
图7、热稳定性对比图
A、本发明ABO3催化剂 B、0.5%钯催化剂
热稳定性指催化剂经800℃气流冲击二小时前后的丙烯净化率(η)变化。废气含丙烯10000ppm,空气10000h-1
Δη热稳=η高温冲击后-η高温冲击前
图8、抗铅性对比图
A、本发明ABO3型催化剂
B、0.5%钯催化剂
抗铅性,指催化剂被铅中毒前后,对丙烯净化率(η)的变化。废气含丙烯10000ppm,废气空速10000h-1
△η抗铅=η铅中毒后-η铅中毒前
图9、钢瓶空气中总碳氢化合物(THC)的净化曲线
钢瓶空气含THC 57ppm,空气空速3500h-1
Claims (7)
1、一种制备含稀土的ABO3型复合氧化物/合金蜂窝体催化剂的方法,其特征在于,它由下列步骤组成:
(1)、将双面轧有小孔,孔边带毛刺状突出物的耐高温、高电阻的铁铬铝或镍铬铝合金带进行除油、酸蚀粗化,并在650℃~750℃的氧化气氛中活化1~2小时;
(2)、使上述合金带在常温下按1~2米/分的速度在0.5~0.6秒之间快速通过按化学计量值配制的催化活性物的盐溶液;
(3)、在110℃~200℃的温度下按与(2)相同的速度快速干燥上述载有催化活性物的合金带;
(4)、在350℃~450℃的温度下进行盐类分解;
(5)、在650℃~850℃的温度下进行氧化处理;
(6)、冷却后绕卷(或排列)成型。
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US5028404A (en) * | 1989-04-25 | 1991-07-02 | University Of Notre Dame Du Lac | Metal oxide catalysts |
FR2665089B1 (fr) * | 1990-07-25 | 1993-11-19 | Stts | Catalyseurs de post-combustion. |
US5622680A (en) * | 1990-07-25 | 1997-04-22 | Specialites Et Techniques En Traitement De Surfaces-Stts | Post-combustion catalysts |
FI89463C (fi) * | 1991-01-03 | 1993-10-11 | Kemira Oy | Anvaendning av en nickelbaserad, aluminium innehaollande metallegering som substratmaterial foer en avgaser renande katalysator |
DE4409625A1 (de) * | 1994-03-21 | 1995-09-28 | Emitec Emissionstechnologie | Verfahren zum Herstellen eines katalytischen Konverters |
US5559073A (en) * | 1994-09-26 | 1996-09-24 | Beijing Huaxia Environmental Protection Company | Pollution control catalyst with mutual protective distributed-active-combinations each including noble-metal-atoms stably structured and protected therein |
CN1091396C (zh) * | 2000-06-21 | 2002-09-25 | 中国科学院兰州化学物理研究所 | 用于净化废气的催化剂 |
IT1319198B1 (it) * | 2000-10-11 | 2003-09-26 | Sued Chemie Mt Srl | Catalizzatori per ossidazione. |
EP2218501A4 (en) * | 2007-10-23 | 2014-01-29 | Cataler Corp | CATALYST FOR PURIFYING EXHAUST GASES |
US20090264283A1 (en) * | 2008-04-16 | 2009-10-22 | Basf Catalysts Llc | Stabilized Iridium and Ruthenium Catalysts |
US20090263300A1 (en) * | 2008-04-16 | 2009-10-22 | Yang Xiaolin D | Stabilized Iridium and Ruthenium Catalysts |
DK2202201T3 (en) * | 2008-12-23 | 2016-08-01 | Clariant Prod (Italia) Spa | Ammoniakoxidationskatalysatorer |
CN103170242A (zh) * | 2013-04-08 | 2013-06-26 | 武汉大学 | 一种有机废气净化方法 |
CN108479386B (zh) * | 2018-05-31 | 2023-12-19 | 深圳市中金岭南科技有限公司 | 一种选择性加热催化处理废气的装置和处理方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US3867313A (en) * | 1970-12-28 | 1975-02-18 | Universal Oil Prod Co | Nickel-free, all metal, catalyst element |
GB1388637A (en) * | 1971-06-02 | 1975-03-26 | Gould Inc | Article for catalytic reduction of nox |
FR2174180A1 (en) * | 1972-03-01 | 1973-10-12 | Hitachi Ltd | Exhaust gases purification - using reducing catalysts contg sintered oxide mixts |
US3905918A (en) * | 1972-09-16 | 1975-09-16 | Heraeus Gmbh W C | Catalyst for purifying exhaust gases |
DE2351237C3 (de) * | 1973-01-30 | 1978-09-14 | Kali-Chemie Ag, 3000 Hannover | Verfahren zur Herstellung eines Katalysators |
DE2425343B2 (de) * | 1973-05-29 | 1978-10-26 | Western Electric Co., Inc., New York, N.Y. (V.St.A.) | Katalysator auf der Basis eines perowskitartigen Seltenen Erdmetall-Manganits und dessen Verwendung |
US4089810A (en) * | 1973-08-20 | 1978-05-16 | Johnson, Matthey & Co., Limited | Catalyst |
FR2279463A1 (fr) * | 1974-04-25 | 1976-02-20 | Du Pont | Compositions catalytiques d'oxydes de metaux |
US4049583A (en) * | 1974-04-25 | 1977-09-20 | E. I. Du Pont De Nemours And Company | Metal oxide catalytic compositions having perovskite crystal structures and containing metals of the platinum group |
GB1568861A (en) * | 1975-10-22 | 1980-06-11 | Atomic Energy Authority Uk | Catalysts |
US4134852A (en) * | 1977-09-02 | 1979-01-16 | The International Nickel Company, Inc. | Process for preparing mixed metal oxide catalysts |
JPS5570348A (en) * | 1978-11-20 | 1980-05-27 | Matsushita Electric Ind Co Ltd | Catalyst element |
JPS5610334A (en) * | 1979-07-06 | 1981-02-02 | Toyota Motor Corp | Catalyst for cleaning up exhaust gas and manufacture of said catalyst |
JPS5610333A (en) * | 1979-07-06 | 1981-02-02 | Toyota Motor Corp | Catalyst for cleaning up exhaust gas and manufacture of said catalyst |
US4331631A (en) * | 1979-11-28 | 1982-05-25 | General Motors Corporation | Enhanced oxide whisker growth on peeled Al-containing stainless steel foil |
JPS58156350A (ja) * | 1982-03-12 | 1983-09-17 | Matsushita Electric Ind Co Ltd | 排ガス浄化装置 |
US4601999A (en) * | 1983-11-09 | 1986-07-22 | William B. Retallick | Metal support for a catalyst |
FR2568143B1 (fr) * | 1984-07-30 | 1986-12-05 | Prod Catalyse Ste Fse | Catalyseur et procede pour le traitement des gaz d'echappement des moteurs a combustion interne |
-
1986
- 1986-07-30 CN CN86105768.6A patent/CN1004992B/zh not_active Expired
-
1987
- 1987-07-14 EP EP87110139A patent/EP0255625B1/en not_active Expired - Lifetime
- 1987-07-14 DE DE3789638T patent/DE3789638D1/de not_active Expired - Lifetime
- 1987-07-27 US US07/078,468 patent/US4820678A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN86105768A (zh) | 1987-11-11 |
EP0255625B1 (en) | 1994-04-20 |
EP0255625A3 (en) | 1988-06-15 |
DE3789638D1 (de) | 1994-05-26 |
EP0255625A2 (en) | 1988-02-10 |
US4820678A (en) | 1989-04-11 |
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