CN107442162A - 一种金属载体活性涂层的制备方法 - Google Patents
一种金属载体活性涂层的制备方法 Download PDFInfo
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- CN107442162A CN107442162A CN201710501324.7A CN201710501324A CN107442162A CN 107442162 A CN107442162 A CN 107442162A CN 201710501324 A CN201710501324 A CN 201710501324A CN 107442162 A CN107442162 A CN 107442162A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000010358 mechanical oscillation Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- 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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- B01D53/34—Chemical or biological purification of waste gases
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本发明涉及一种金属载体活性涂层的制备方法，其特征在于具有活性组分负载均匀、负载率高，涂层与载体结合的牢固度高，发动机台架测试显示在205～518℃，NOx转化率高达98.3%，表现出较好NOx活性。此外，本发明制备工艺过程简单，便于工业化连续生产。
Description
技术领域
本发明涉及一种金属载体活性涂层的制备方法，属于汽车排放技术领域，尤其属于SCR脱硝的催化剂制备领域。
背景技术
为满足NOx排放法规，机内净化及后处理技术必不可少，目前， SCR技术已成为中重型柴油机企业首选降低 NOx技术路线，其原理是利用尿素水解产生的氨气和汽车尾气中的NOx经过涂有活性涂层的载体时，NOx快速被氨气还原为氮气和水，氨气和NOx之所以能够在后处理载体上进行快速的化学反应，是与载体组成密不可分的。带有活性涂层载体是由载体和催化剂构成，载体首先承担着涂层和活性组分，其次还提供合适的催化反应通道，没有载体的支撑，仅仅是催化剂粉末是无法发挥其催化性能的，金属载体催化器具有背压低、承受机械振动性能强、有效催化面积大、达到相同的转换率所用催化器体积小、能很快达到催化剂起燃工作温度等特性，在汽车尾气脱硝领域展现了优越的性能。催化剂作为脱硝的主要活性组分，必须负载到载体上才能发挥作用，因此如何将催化剂与载体有机结合，使其脱硝效果达到最佳是目前研究的热点。
发明专利CN201110048031.0公开了一种用于固定源尾气脱硝的蜂窝状金属丝网催化剂及制备，提供了催化剂载体由附着氧化铝涂层的平板状和瓦楞状金属丝网相互交替堆积并固定成型,载体内部通道具有三维通透结构,其特征在于,催化剂是通过分步负载的方法将活性组分V2O5、WO3和TiO2负载于催化剂载体表面制备的,V2O5、WO3和TiO2的质量之和为氧化铝涂层和V2O5-WO3-TiO2总重量的10％～70％,V元素的质量为V2O5、WO3和TiO2质量之和的0.2％～5.6％。本发明具有低温脱硝活性和低温抗硫抗水性能,当烟气温度为250℃、SO2浓度为600ppm、水分含量为10％时,催化剂脱硝效率达到90％以上。
发明专利CN 201510111018.3 公开了一种金属载体上分子筛涂层的制备方法，金属载体以稀硝酸超声振荡清洗干燥后控制焙烧气氛中含氧量进行预处理。HZSM-5分子筛以柠檬酸和蒸馏水于刚玉球磨机中先预粘化，再与B型氧化铝粉和小孔拟薄水铝石粉以稀硝酸胶化的粘合物混合，加水和柠檬酸后球磨制浆。浆料使用前控制pH值为6.8～7.0。金属载体负载浆料采用浸涂法，以吹扫或抽吸使浆料涂覆均匀并达到负载量要求。金属载体上负载的HZSM-5分子筛涂层脱落率≤5.0%。本发明实现在金属载体上使分子筛涂覆大量化，附着强度好，能一次性涂覆达到负载量要求，生产工艺简单，与现有机动车三效催化剂生产设备兼容性好。
发明专利CN200410041178.7 涉及提供一种金属蜂窝载体催化剂的制备方法，该方法制备的金属蜂窝载体催化剂的涂层不易脱落，起燃性能好，具有较高的三效催化剂活性，可同时净化排气中的CO、HC、NOx，有较宽的可操作窗口。该金属蜂窝载体催化剂的制备主要是以镍铬不锈钢蜂窝(简称为金属蜂窝载体)作为第一载体，活性氧化铝粉为第二载体，另外还添加少量稀土元素的氧化物如CeO。
上述制备脱硝催化剂的制备方法存在问题如下：（1）活性组分涂覆不均匀,局部发生富集或者涂覆量过少；（2）活性组分涂层与载体结合的牢固度低，涂层易脱落；（3）催化剂温度窗口窄；（4）制备工艺复杂。
发明内容
本发明的目的在于提供一种金属载体活性涂层的制备方法，具有活性组分负载均匀、负载率高，涂层与载体结合的牢固度高，发动机台架测试显示在205～518℃，NOx转化率高达98.3%，表现出较好NOx活性。此外，本发明制备工艺过程简单，便于工业化连续生产。
本发明的技术方案是这样实现的：一种金属载体活性涂层的制备方法，其特征在于具体步骤如下：(1)金属载体前处理：将载体520℃煅烧2h～4h，待室温下浸泡在质量分数为2.8%～5.3%的盐酸中超声20min～40min后，取出载体，用去离子水反复冲洗至PH呈中性后烘干；（2）活性浆液制备：a.将6.1～7.9份铜盐、4.6～7.3份铁盐、2.2～3.7份金属助剂盐溶于去离子水中，搅拌溶解；b.加入18.4～22份分子筛载体、0.4～0.6份氨基甲酸铵，45～60℃下，搅拌2～4h；c.加入0.39～0.70份玻璃纤维、12.8～19份粘结剂、2.6～6.0份表面分散剂，直至搅拌均匀得到活性浆液；（3）金属载体的活化：将处理过的金属载体置于配制好的活性浆液中浸渍5～10min后，取出，用吹扫气体吹走表面残留液，置于烘箱85～110℃烘干，如此反复，采用吹扫和恒温烘干的手段连续负载1～3次，最后在480℃～550℃煅烧2～4h。
所述金属助剂为La、Mn、Co、Ce盐中的一种或几种.
所述粘结剂为黏土、硅溶胶、铝溶胶及羧甲基纤维素钠的混合物，分散剂为无水乙醇、丙醇中的一种或组合。
本发明积极效果是将有铜铁离子、过渡金属离子溶液与分子筛进行反应，在一定温度下通过氨基甲酸铵的作用下，使金属离子与分子筛达到最佳置换反应，然后再经高温煅烧使分子筛、活性金属组分通过化学作用，在金属载体表面实现活性型组分分布均匀、高效率负载；添加硅溶胶、铝溶胶及羧甲基纤维素的粘结剂体系，一方面为了保证整个体系的粘度，另一方面即使高温煅烧后部分铝溶胶和硅溶胶仍然能发挥作用，进而使活性组分牢固地负载在金属载体表面。添加的玻璃纤维，能够提高活性液的负载量。
附图说明
图1为实施例1制备一种金属载体活性涂层的脱落率测试在振动试验台安装示意图。
具体实施方式
在下述的具体事例描述中，给出了大量具体的细节以便于更为深刻的理解本发明。然而，对于本领域技术人员来说显而易见的是，本发明可以无需一个或多个这些细节而得以实施。
实施例1
(1) 金属载体前处理：将金属载体520℃煅烧4h，待室温下超声浸泡在质量分数为2.8%的盐酸中20min，取出载体，用去离子水反复冲洗至PH呈中性后，烘干；
（2）活性浆液制备：a. 将350g硝酸铜、260g硝酸铁、125g硝酸铈溶于2500g去离子水中，搅拌溶解；b.加入1200gSapo34分子筛、27.6g氨基甲酸铵，45℃搅拌4h；c.加入38g玻璃纤维、20g黏土、380g硅溶胶(SiO2含量为40%)、430g铝溶胶（Al2O3含量为40%）、180g质量分数1%羧甲基纤维素钠、150g无水乙醇，搅拌均匀得到活性浆液；
（3）金属载体的活化：将处理过的金属载体称重后置于配制好的活性浆液中浸渍5min后,取出，用吹扫气体吹走表面残留液，置于烘箱85℃烘干，如此反复，共进行二次涂覆,480℃煅烧4h，称其重量，经计算负载率为35.2%，由此可见负载率较高。
将实施例1制备得到金属载体活性涂层载体进行涂层脱落率试验，首先称量质量后将金属载体活性涂层载体安装在振动试验台上，如图1所示。采用振动加速度10g，振动频率为（100±5）Hz，试验时间为5h，实验结束后取下载体催化剂称其质量，经计算涂层脱落率为3.23%，这表明活性组分涂层与载体结合的牢固度高，解决了涂层易脱落问题。
将实施例1制备得到金属载体活性涂层载体进行发动机台架试验，实验条件及测试结果如表1所示。
表1
可以看出A75工况下NOx转化率最高为98.3%，C50工况下NOx转化率最低为79.3%，其他工况NOx转化率均能达到84%以上，在205～518℃显示了很好NOx活性。
实施例2
(1) 金属载体前处理：将金属载体520℃煅烧4h，待室温下超声浸泡在质量分数为5.3%的盐酸中40min，取出载体，用去离子水反复冲洗至PH呈中性后，烘干；
（2）活性浆液制备：a. 将480g硝酸铜、415g硝酸铁、150g硝酸镧溶于2300g去离子水中，搅拌溶解；b.加入1200gSSZ-13分子筛、35.1g氨基甲酸铵，60℃搅拌2h；c. 加入42g玻璃纤维、45g黏土、290g硅溶胶(SiO2含量为40%)、400g铝溶胶（Al2O3含量为40%）、350g质量分数1%羧甲基纤维素钠、365g无水乙醇，搅拌均匀得到活性浆液；
（3）金属载体的活化：将处理过的金属载体，置于配制好的活性浆液中浸渍10min后,取出，用吹扫气体吹走表面残留液，置于烘箱110℃烘干，如此反复进行第二，三次浸渍,最后在550℃煅烧2h。
实施例3
(1) 金属载体前处理：将金属载体520℃煅烧4h，待室温下超声浸泡在质量分数为3.5%的盐酸中30min，取出载体，用去离子水反复冲洗至PH呈中性后，烘干；
（2）活性浆液制备：a. 350g硝酸铜、320g硝酸铁、200g硝酸锰溶于2600g去离子水中，搅拌溶解；b.加入1200gBeta25分子筛、26g氨基甲酸铵，60℃搅拌3h；c. 加入32g玻璃纤维、18g黏土、280g硅溶胶(SiO2含量为40%)、360g铝溶胶（Al2O3含量为40%）、180g质量分数1%羧甲基纤维素钠、215g无水乙醇，搅拌均匀得到活性浆液；
（3）金属载体的活化：将处理过的金属载体置于配制好的活性浆液中浸渍8min后，取出，用吹扫气体吹走表面残留液，置于烘箱105℃烘干，最后在550℃煅烧2h。
实施例4
(1) 金属载体前处理：将金属载体520℃煅烧4h，待室温下超声浸泡在质量分数为5.3%的盐酸中40min，取出载体，用去离子水反复冲洗至PH呈中性后，烘干；
（2）活性浆液制备：a.将450g硝酸铜、480g硝酸铁及205g硝酸钴溶于3000g去离子水中，搅拌溶解；b.加入1200gZSM5分子筛、37.1g氨基甲酸铵，55℃搅拌2h；c.加入32g玻璃纤维、20g黏土、280g硅溶胶(SiO2含量为40%)、350g铝溶胶（Al2O3含量为40%）、290g质量分数1%羧甲基纤维素钠、195g无水乙醇，搅拌均匀得到活性浆液；
（3）金属载体的活化：将处理过的金属载体置于配制好的活性浆液中浸渍5min后,取出，用吹扫气体吹走表面残留液，置于烘箱110℃烘干，如此反复进行第二次涂覆,最后在550℃煅烧2h。
实施例5
(1) 金属载体前处理：将金属载体520℃煅烧4h，待室温下超声浸泡在质量分数为3%的盐酸中30min，取出载体，用去离子水反复冲洗至PH呈中性后，烘干；
（2）活性浆液制备：a. 400g硝酸铜、350g硝酸铁、80g硝酸铈、80g硝酸镧、80g硝酸锰、80g硝酸钴溶于3000g去离子水中，搅拌溶解；b.加入1200gBeta40分子筛、40g氨基甲酸铵，55℃搅拌2h；c.加入25g玻璃纤维、26g黏土、295g硅溶胶(SiO2含量为40%)、360g铝溶胶（Al2O3含量为40%）、290g质量分数1%羧甲基纤维素钠、175g无水乙醇，搅拌均匀得到活性浆液；
（3）金属载体的活化：将处理过的金属载体称重后置于配制好的活性浆液中浸渍8min后,取出，用吹扫气体吹走表面残留液，置于烘箱105℃烘干，最后在550℃煅烧3h，取出称重，经计算负载率为27.8%。
Claims (3)
1.一种金属载体活性涂层的制备方法，其特征在于具体步骤如下：(1)金属载体前处理：将载体520℃煅烧2h～4h，待室温下浸泡在质量分数为2.8%～5.3%的盐酸中超声20min～40min后，取出载体，用去离子水反复冲洗至PH呈中性后烘干；（2）活性浆液制备：a.将6.1～7.9份铜盐、4.6～7.3份铁盐、2.2～3.7份金属助剂盐溶于去离子水中，搅拌溶解；b.加入18.4～22份分子筛载体、0.4～0.6份氨基甲酸铵，45～60℃下，搅拌2～4h；c.加入0.39～0.70份玻璃纤维、12.8～19份粘结剂、2.6～6.0份表面分散剂，直至搅拌均匀得到活性浆液；（3）金属载体的活化：将处理过的金属载体置于配制好的活性浆液中浸渍5～10min后，取出，用吹扫气体吹走表面残留液，置于烘箱85～110℃烘干，如此反复，采用吹扫和恒温烘干的手段连续负载1～3次，最后在480℃～550℃煅烧2～4h。
2.根据权利要求1中所述的一种金属载体活性涂层的制备方法，其特征在于所述金属助剂为La、Mn、Co、Ce盐中的一种或几种。
3.根据权利要求1中所述的一种金属载体活性涂层的制备方法，其特征在于所述粘结剂为黏土、硅溶胶、铝溶胶及羧甲基纤维素钠的混合物，分散剂为无水乙醇、丙醇中的一种或组合。
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