CN1015964B - 用于还氮氧化物的氧化锆/沸石催化剂 - Google Patents

用于还氮氧化物的氧化锆/沸石催化剂

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Publication number
CN1015964B
CN1015964B CN87100737A CN87100737A CN1015964B CN 1015964 B CN1015964 B CN 1015964B CN 87100737 A CN87100737 A CN 87100737A CN 87100737 A CN87100737 A CN 87100737A CN 1015964 B CN1015964 B CN 1015964B
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catalyst
zeolite
zirconia
described catalyst
nitrogen
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CN87100737A (zh
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威廉姆·H·格迪斯
查理斯·利姆
索马斯·茨曼斯基
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Saint Gobain Abrasives Inc
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Norton Co
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

一种用来在有氨存在下将氧化氮选择性地还原为氮的催化剂，该催化剂是由一种混合物形成的实体。该混合物合有氧化锆(5-50%(重))，沸石(50-90%)，粘合材料(0-30%)，根据情况，还可含有至少为0.1%(重)的选自钒和铜的氧化物的助催化剂。

Description

在所有的矿物燃料的燃烧过程中都产生氮氧化物（NOx）。由于这些NOx排放物可能是产生酸雨的原因，以及人们对这一问题日益清楚的认识，从而促进了降低NOx向大气排放的催化材料的研究。
美国专利4，220，632和3，895，094号公开了在氨或其它还原剂的选择催化还原中使用沸石。美国专利4085193号公开了在二氧化钒或其它金属氧化物的存在下使用二氧化钛来达到同样的目的。美国专利4，473，535公开了用于同样目的的铜置换沸石（丝光沸石）。总之，近年来有很多已颁专利公开了降低废气中NOx含量的方法。由于很多含有NOx的气流同时也含有对选择催化还原催化剂的性能有不利影响氧化硫（SOx），因而非常期望有一种能抗SOx毒害的SCR催化剂。本发明就是涉及了在废气气流，特别是含有SOx的废气气流中，在还原气体（例如氨）的存在下，用来选择催化还原（SCR）氮的氧化物的改进催化剂。
我们发现，具有改进的效率和抗SOx中毒性的NOx选择催化还原催化剂，可以通过将高表面积的氧化锆和天然或合成沸石混合在一起来制备。将这些材料混合、成型、干燥并焙烧制成希望的形状，例如环状或蜂窝状，其间可加入，也可不加入陶瓷粘合材料。焙烧的温度低于沸石能形成一个整体的稳定极限。氧化锆起始材料的表面积（以B.E.T.方法测量）应至少为每克10平方米，最好大于每克50平方米。氧化锆粉末以来自锆盐的水解产品为宜。
氧化锆在产品中推荐的数量是10-30%（重）。但根据其它因素的不同，氧化锆的有效率数量可以为5-50%。沸石的数量应为50-90%。粘合剂的数量为0-30%。
所述催化剂可以通过添加少量呈母体形态的氧化钒和/或氧化铜和/或其它碱金属氧化物助催化剂来进一步强化。为了使催化剂在有二氧化硫存在时有最好的稳定性，最好加入钒。
推荐的沸石是天然斜发沸石（可能和其它沸石如菱沸石结合在一起）。沸石在催化剂产品中应主要以酸的形式存在，或者可以加热转化为酸的形式。
这种形式可以直接通过酸置换来产生，或者可以间接地先用铵置换，然后再加热除去氨，并将材料转化为氢型。
用于本发明的沸石是可以用上述任一方法制成氢型，并且在氢型下稳定的沸石。某些沸石如沸石A和钠沸石在酸形式下是不稳定的所以在本发明中是无效的。可以通过氨和/或酸置换来制备的沸石的例子为丝光沸石、斜发沸石、毛沸石、片沸石和镁碱沸石。最好或只能用铵置换方法来制备的沸石是天然八面沸石和其对应合成物沸石Y，菱沸石和钠菱沸石。
也可以应用沸石的混合物。其它氢型沸石，例如ZSM系列的沸石，可以通过有机模板的热分解来制备，并且也适宜用在本发明的催化组合物中。
在使用中，使含有诸如氨的合适还原气体的废气在催化剂上通过。根据具体用途的不同要求，催化剂可以制成蜂窝状，叠置起来并且安排（如果较多的话）形成一个气体流的通道。
或者，该催化剂的形式也可以是任意堆放的鞍状物、环、星状物、十字环、球、片、或者聚集块，或者将该活性催化剂组合物涂敷在合适的基材上，例如涂在堇青石或其它陶瓷或金属的蜂窝状物上。已处理的烟道气应该至少为200℃以便避免铵盐的沉积。该烟道气的温度可高达650℃。空速不是很严格，但典型的时空速为10000（气体的体积是在标准状态下计算的）。在350℃下1600ppm的NOx含量可以减少90%以上。
实施例
催化剂的制备
用下列方法制备用来制造公称直径为1/4英寸，园孔直径为1/8英寸的环的组合物，即将4000克铵型斜发沸石的干燥粉末与1050克表面积约为90平方米/克的化学沉淀的二氧化锆混合在一起。然后加水1800ml，并继续混合10分钟。
加106ml浓硝酸，并且再混合10分钟。可以再加入额外的水来调节混合物的稠度。当该混合物进行挤出时，在混合物润湿后可加入0.2%的有机阳离子聚合物挤出助剂。
挤出后，将环在200°F下，在空气气氛中干燥1-2小时，最后的焙烧是在1000°F下进行的，时间为5小时。当需要向组成物中加入钒或铜时，该助催化剂母体可以在混合操作中加入，或者将该助催化剂母体浸入焙烧后的成形产品。作为氧化物（V2O5或CuO加入的助催化剂的数量按元素计算应至少为0.1%。
按照上述实施例的方法，制备各种产品。
表Ⅰ表示了按上述制备的各种催化剂的组成，其中的沸石、氧化锆、粘合剂和助催化剂的数量是不同的。
SO2的浓度是随时间变化的。在气流中没有SO2存在的情况下在24小时的时间里测催化剂量的NOx还原活性。（其结果列于表Ⅱ，第2栏中）。然后向气流中加入50ppm SO2，并在24小时后测量NOx的脱除效率（结果列于第3栏）。然后，将SO2的浓度增加至1600ppm，并在24、48和33小时测量NOx脱除效率（结果分别于第4，5，6栏）。
测试条件为：
温度（℃）    350
氧气浓度（体积%）    5
NOx浓度（体积ppm）    500
NH3/NOx（体积） 1
H2O 15
N2余量
SO2如上所述
表Ⅱ的数据清楚地表明，本发明的含锆催化剂（样品65411号）比对于比样（样品65233号）更好。含锆催化剂不仅在无SO2时有更高的初始活性，而且更重要的是在SO2为1600ppm时，还具有较高的活性。
表Ⅰ
选择催化还原催化剂的组成
样品号 沸石 ZrO2粘合剂
65233    90    0    10
65426    0    100    0
65411    80    20    0
＊对比
表Ⅱ
选择催化还原催化剂在接触SO2之前和之后的NOx脱除效率
样品号 初始脱除 在和50ppm SO2在和1600ppm的SO2接触
百分数    接触后24小时后    后脱除的NOx百分数
NOx的脱除百
分数    24小时    48小时    33小时
65233＊    72.1    63.9    57.4    47.4    -
65246    9.1    18.2    -    -    -
65411    96.0    84.0    82.0    82.0    81.7
＊对比

Claims (9)

1、一种用来在氨存在下将NOx选择性还原为氮的催化剂，该催化剂是一种含有5-50%(重)的表面积至少为10平方米/克的氧化锆起始材料的有一定形状的混合物，该催化剂还含有50%-90%的一种或多种氢型或铵型沸石和0-30%的粘合剂。
2、权利要求1所述的催化剂，当该催化剂含多种氢型或铵型沸石时，其中的沸石主要含斜发沸石。
3、权利要求1所述的催化剂，当该催化剂仅含一种沸石时，该沸石是斜发沸石。
4、权利要求1所述的催化剂，其中所述的氧化锆是由锆盐水解而衍生的。
5、权利要求1所述的催化剂，其中所述的氧化锆是由一种或多种锆盐衍生的ZrO2。
6、权利要求1-5中任何一项所述的催化剂，该催化剂含有至少0.1%的钒氧化物或铜氧化物助催化剂。
7、权利要求1-5中任何一项所述的催化剂，其中活性催化剂组合物涂敷在金属或陶瓷载体上。
8、权利要求1-5中任何一项所述的催化剂，其中所述的氧化锆起始材料的表面积至少为50平方米/克。
9、权利要求1-5中任何一项所述的催化剂，该催化剂可为环形、球形、十字形、星形、鞍形、聚集块、蜂窝形或片状。
CN87100737A 1986-02-18 1987-02-18 用于还氮氧化物的氧化锆/沸石催化剂 Expired CN1015964B (zh)

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US06/829,884 US4735930A (en) 1986-02-18 1986-02-18 Catalyst for the reduction of oxides of nitrogen
US829884 1986-02-18
US829,884 1986-02-18

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EP (1) EP0234441B1 (zh)
JP (1) JPH0712436B2 (zh)
KR (1) KR950002222B1 (zh)
CN (1) CN1015964B (zh)
AT (1) ATE65935T1 (zh)
AU (1) AU594118B2 (zh)
BR (1) BR8700731A (zh)
CA (1) CA1285546C (zh)
DE (1) DE3771889D1 (zh)
FI (1) FI86513C (zh)
NO (1) NO170716C (zh)
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EP0234441B1 (en) 1991-08-07
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JPH0712436B2 (ja) 1995-02-15
CN87100737A (zh) 1987-11-04
ZA871029B (en) 1987-08-04
ATE65935T1 (de) 1991-08-15
NO170716C (no) 1992-11-25
FI870659A0 (fi) 1987-02-17
NO870616D0 (no) 1987-02-17
EP0234441A3 (en) 1988-11-09
KR870007723A (ko) 1987-09-21
NO170716B (no) 1992-08-17
US4735930A (en) 1988-04-05
KR950002222B1 (ko) 1995-03-15
JPS62193649A (ja) 1987-08-25
AU594118B2 (en) 1990-03-01
NO870616L (no) 1987-08-19
CA1285546C (en) 1991-07-02
FI870659A (fi) 1987-08-19
BR8700731A (pt) 1987-12-15
DE3771889D1 (de) 1991-09-12
EP0234441A2 (en) 1987-09-02

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