CN106475097A - 用于在高温下氮氧化物还原的scr催化剂 - Google Patents
用于在高温下氮氧化物还原的scr催化剂 Download PDFInfo
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- CN106475097A CN106475097A CN201610735408.2A CN201610735408A CN106475097A CN 106475097 A CN106475097 A CN 106475097A CN 201610735408 A CN201610735408 A CN 201610735408A CN 106475097 A CN106475097 A CN 106475097A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002360 explosive Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- -1 iron ion Chemical class 0.000 claims description 5
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
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- 229910017435 S2 In Inorganic materials 0.000 claims 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于在高温下氮氧化物还原的SCR催化剂。提供用于产生用于氮氧化物的选择性催化还原的铜沸石催化剂的方法，其中方法包括所提供的沸石基体的酸处理、沸石基体的煅烧和铜离子以及任选地进一步金属离子的后续引入，并且其中在高于700℃下的煅烧在这些步骤之间实施。方法可以利用纯净的沸石基体或已经包含铜的沸石基体来实施。也提供通过该方法产生的催化剂和相应的排气后处理系统。
Description
技术领域
本发明涉及用于利用含铜沸石基体来生成旨在用于氮氧化物的具体催化还原的催化剂的方法。
背景技术
氮氧化物是对环境有严重影响的排气成分。氮氧化物的主要来源是燃烧过程，尤其是内燃发动机中，但是也包括在燃煤、燃油、燃气燃烧器中，其中，氮氧化物在高温区域中形成。理想地，氮氧化物在接近排气形成的地方从燃烧期间产生的排气中被直接移除。
欧洲或北美的环境标准要求带有低氮氧化物排放的清洁机动车辆，如在欧6标准或欧7标准中所要求的。没有带有氮氧还原催化剂的恰当排气后处理系统不能满足这样的要求。相应的常规催化剂必须在低温(150℃-300℃)下有效还原氮氧化物。然而，频繁地，较高的温度在排气风道中占优势。因此，将期望具有在较高的温度下起作用的恰当的催化剂。这些催化剂也应该具有长的使用期限，理想地和它们所被安装在其中的机动车辆的使用期限一样。这特别地应用到被布置在微粒过滤器空间附近中的催化剂，尤其是柴油微粒过滤器，柴油微粒过滤器的再生可导致高达900℃的高温。常规氮氧化物还原催化剂(EP 2 308596 A1、US 5,254,322)在这样的高温下的作用经历严重的退化。
因此，目标是提供一种在高温下(elevated temperature)也有效地且可靠地起作用的氮氧化物还原催化剂。
发明内容
本发明的目标通过以下描述的方法来实现。本发明的进一步有利的实施例可以从进一步的描述、附图和示例性实施例推断。
本发明的第一方面涉及用于产生用于氮氧化物的选择性催化还原的铜沸石催化剂的方法，包括以下步骤：
S1)提供沸石基体，
S2)利用柠檬酸酐溶液处理所述沸石基体，
S3)煅烧所述沸石基体，
S4)利用柠檬酸铜溶液处理所述沸石基体，
其中，煅烧是在高于700℃的温度下实施的。
本发明是有利的，因为以该方式产生的催化剂在宽广的温度范围内还原氮氧化物且在高达900℃温度的水热条件下是稳定的。
沸石基体是例如市售的沸石材料。在步骤S2中利用柠檬酸酰溶液的处理导致酸性中心的形成。煅烧使样品脱铝(dealuminate)。已经出人意料地发现，高于700℃的煅烧，可能特别地产生温度稳定催化剂，所述温度稳定催化剂在从600℃至900℃的范围中的温度起作用且稳定。步骤S3中的处理将铜离子引入到沸石基体中，以获得有利的双功能的、催化高活性的中心。
在根据本发明的方法的优选实施例中，在步骤S1中提供的沸石基体已经包括铜离子。因此，有利地是，也可能使用从一开始就已经包括铜离子且有利地根据本发明的方法改性的沸石材料来产生催化剂。这里，铜离子在步骤S2中从沸石基体中移除。
根据本发明的方法的步骤S2优选地利用0.001-0.04M溶液来实施。该摩尔浓度同样地出人意料地对催化剂的效力起作用，所述催化剂利用沸石材料产生且在从600℃至900℃的范围中的温度起作用且稳定。
根据本发明的方法中的步骤S2和步骤S3优选地各自实施持续一个小时。
进一步优选地是，如果柠檬酸溶液附加地使用在根据本发明的方法中的步骤S2中。在进一步的替代实施例中，铵离子可以附加地使用在步骤S2中的溶液中。
其他金属离子的柠檬酸盐优选地使用在根据本发明的方法中的步骤S4中。这些从包括镁、钙、锶、镧、镨、硼和锆的离子的组中选定。如果使用镁，优选地，附加地使用铁离子或铈离子。
本发明的第二方面涉及带有已经通过根据本发明的方法产生的含铜沸石基体的用于选择性催化还原的催化剂。这里的催化剂的优势对应于根据本发明的方法中的那些。
本发明的第三方面涉及用于内燃发动机的排气后处理系统，其包含根据本发明的催化剂。
微粒过滤器优选地附加地布置在根据本发明的排气后处理系统中，其中催化剂布置在微粒过滤器的上游或下游，或与微粒过滤器布置在一起。
根据本发明的排气后处理系统优选地附加地被构造成将氨引入到排气流中。
附图说明
借助以下附图更详细地解释本发明，其中：
图1示出根据本发明的带有排气后处理系统的装置。
图2示出根据本发明的方法的一个实施例的流程图。
图3以描绘氮氧化物还原与温度的关系的图表示出根据本发明的催化剂的催化活性。
图4以描绘氮氧化物还原与温度的关系的图表示出与商用催化剂相比的根据本发明的催化剂的催化活性。
附图标记列表
1＝装置
2＝内燃发动机
2a＝汽缸
3＝进气道
4＝排气道
5＝排气后处理设备
6＝第一催化设备
6a＝氮氧化物存储催化剂
7＝第二催化设备
7a＝用于选择性催化还原的催化剂
8＝微粒过滤器
具体实施方式
根据图1的图表，带有进气道3和排气道4的内燃发动机2被布置在装置1中。内燃发动机2特别是自动点火内燃发动机。排气后处理设备5布置在内燃发动机2下游的排气道4中。排气后处理设备5包括第一催化设备6，第一催化设备6可包括一个或多个不同的催化剂，例如氮氧化物存储催化剂6a、氧化催化剂和/或三元催化剂。排气后处理设备5另外还包括第二催化设备7，第二催化设备7特别地包括用于选择性催化还原7a的催化剂，其中，例如存储在氮氧化物存储催化剂6a中的氮氧化物能够被还原。微粒过滤器8布置在第一催化设备6和第二催化设备7之间。特别地，微粒过滤器8为柴油微粒过滤器。微粒过滤器8也可以布置在排气道4中的另一位置处，例如，催化设备中的一个之中或第二催化设备7下游。
用于选择性催化还原7a的催化剂为整块类型(monolithic type)，其材料是市售的。它理想地具有蜂窝状结构的基底，所述基底包括含沸石催化剂材料的载体涂层(washcoat)。基底理想地由诸如陶瓷的耐热材料(例如，堇青石)制成，但是也能够由金属或催化活性材料组成，例如，被成形为整块石料的沸石。
催化剂7a的沸石材料特别是利用铜离子改性。它也可以附加的包含镁、钙、锶、镧、镨、硼和锆。如果使用了镁，材料可附加地包含铁离子，或替代性地铈离子。
催化活性载体涂层主要由沸石基体组成，但是也可由其他多微孔硅铝酸盐基材料组成。
用于氮氧化物的选择性催化还原的主要包括铜改性的沸石的催化剂根据图2的方法而产生，其中在第一步骤S1中提供沸石基体。在优选的替代实施例中，提供已经包含铜离子的沸石基体。在第二步骤S2中，利用0.001-0.04M柠檬酸酐溶液处理沸石基体。铵离子在这里可以添加至柠檬酸酰溶液。在替代实施例中，也可以附加地使用柠檬酸溶液。此外，仅使用柠檬酸溶液或带有柠檬酸氢二铵的柠檬酸溶液也是可能的。在替代实施例中，也可以在步骤S2中使用柠檬酸氢铵和柠檬酸氢二铵的溶液。同样地可以想到二羧酸或三羧酸、苯甲酸或乙二胺四乙酸(EDTA)。步骤S1中的酸处理在97℃下优选地实施30分钟，同样地优选地实施60分钟。酸处理之后，利用蒸馏水重复地冲洗材料，且然后在100℃下干燥。
在第三步骤S3中，沸石基体通过在700℃下煅烧持续一个小时而被煅烧，优选地在700℃以上且特别是优选地在800℃下。持续时间也可以长于一个小时。
在第四步骤S4中，利用柠檬酸铜溶液处理所煅烧的沸石基体。也可以使用如在步骤S2中所描述的另一溶液。理想地，步骤S4中的处理在和关于如在步骤S2中的溶液的摩尔浓度、持续时间和温度相同的条件下进行。最后，利用蒸馏水重复冲洗富集铜离子和/或其他金属离子的沸石基体，且在100℃下进行干燥。
为了展示催化性能，在如文献EP 2308596 A1中所描述的条件下试验使用所描述的方法产生的催化剂。所生成的催化剂和参考催化剂(市售的铜沸石)被布置成堇青石整料上的载体涂层，小量的氧化铝被用作粘合剂。在试验之前，全部催化剂利用10vol.％的水和10vol.％的氧气在氮环境中在600℃下进行一小时并然后在800℃下进行一小时的水热预处理。图3示出关于催化活性的比较试验，其中，市售铜沸石催化剂(催化剂A)的还原性能在高于600℃、特别是在高于700℃的高温的氮环境中550ppm一氧化氮、600ppm氨(或α＝1.2至4；α值指示氨相对氮氧化物的比)、10vol.％氧气、10vol.％氢气的反应混合物中从160℃至750℃的温度范围内且在气时空速SV＝30000h-1的条件下急剧下降。通过改变添加的氨(α＝1.2至4)或尿素的量能够在有限的范围实现氮氧化物还原的一定程度的增加(见图3中的图解)。
图4清晰地示出，根据本发明的催化剂(催化剂B)在高于600℃的温度，尤其是高于700℃的温度，与正常添加氨(α＝1.2)的常规催化剂(催化剂A)相比还原多于两倍量的氮氧化物。因此已经通过示例示出，已经使用根据本发明的方法产生的根据本发明的催化剂相比常规催化剂在高温下实质上更加稳定且高效。
Claims (13)
1.一种用于产生用于氮氧化物的选择性催化还原的铜沸石催化剂的方法，包括以下步骤：
S1)提供沸石基体，
S2)利用柠檬酸酐溶液处理所述沸石基体，
S3)煅烧所述沸石基体，
S4)利用柠檬酸铜溶液处理所述沸石基体，
其中，煅烧是在高于700℃的温度下实施的。
2.根据权利要求1所述的方法，其中步骤S1中的所述沸石基体已经包含铜离子。
3.根据权利要求2所述的方法，其中步骤S2利用0.001-0.04M溶液实施。
4.根据前述权利要求1-3中的一项所述的方法，其中步骤S2和步骤S3各自实施一个小时。
5.根据前述权利要求1-3中的一项所述的方法，其中柠檬酸溶液附加地使用在步骤S2中。
6.根据前述权利要求1-3中的一项所述的方法，其中铵离子附加地使用在步骤S2中的所述溶液中。
7.根据前述权利要求1-3中的一项所述的方法，其中柠檬酸盐或其他金属离子附加地使用在步骤S4中的所述溶液中。
8.根据权利要求7所述的方法，其中所述金属离子从包括镁、钙、锶、镧、镨、硼和锆的离子的组中选定。
9.根据权利要求7或8所述的方法，其中使用金属离子镁且附加地使用铁离子或铈离子。
10.一种带有通过权利要求1-9中的一个的所述方法产生的含铜沸石基体的催化剂。
11.一种用于内燃发动机(2)的排气后处理系统(5)，其包括根据权利要求10所述的催化剂。
12.根据权利要求11所述的排气后处理系统(5)，其中，微粒过滤器(8)附加地布置，且所述催化剂布置在所述微粒过滤器(8)的上游或下游或者与所述微粒过滤器(8)布置在一起。
13.根据权利要求11或12所述的排气后处理系统(5)，所述排气后处理系统(5)被附加地构造成将氨引入到排气流中。
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| CN102029175A (zh) * | 2009-10-07 | 2011-04-27 | 福特环球技术公司 | 选择性催化还原剂及其制备方法 |
| CN102614875A (zh) * | 2011-01-26 | 2012-08-01 | 福特环球技术公司 | 用于组合lnt-scr应用的lnt和scr催化剂 |
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| WO2014203048A1 (en) * | 2013-06-21 | 2014-12-24 | Everest Instruments Pvt. Ltd. | Photocatalytic composition for environmental purification and method thereof |
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| CN102029175A (zh) * | 2009-10-07 | 2011-04-27 | 福特环球技术公司 | 选择性催化还原剂及其制备方法 |
| CN102614875A (zh) * | 2011-01-26 | 2012-08-01 | 福特环球技术公司 | 用于组合lnt-scr应用的lnt和scr催化剂 |
| CN103157505A (zh) * | 2013-03-25 | 2013-06-19 | 中国科学院生态环境研究中心 | 一种Cu-SSZ-13催化剂、制备方法及其用途 |
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