CN102985179A - 废气脱硝催化剂用金属基材的制造方法 - Google Patents
废气脱硝催化剂用金属基材的制造方法 Download PDFInfo
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- 239000003546 flue gas Substances 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 45
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- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
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- 229910001566 austenite Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
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- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明提供提高价格低、容易稳定供给的SUS430基材的耐腐蚀性，能够与SUS304同样地不会腐蚀地使用的废气脱硝催化剂用金属基材。废气脱硝催化剂用金属基材的制造方法，对于对铁素体系不锈钢带状钢板进行了金属板网加工的带状金属板网基材，连续进行（1）对附着于该基材的加工油进行脱脂的工序、（2）使基材潜入含磷酸和表面活性剂的溶液内而负载该溶液的工序、（3）对剩余的前述溶液进行除液的工序和（4）将负载了前述溶液的基材干燥和加热而使磷酸与基材反应的工序，在前述基材表面形成耐腐蚀性的磷酸化合物被膜。
Description
技术领域
本发明涉及废气脱硝催化剂用金属基材的制造方法，特别是在用于负载有催化剂成分的板状催化剂的金属制网状基材表面以低价、适合大量生产的方法形成能够防止硫氧化物（SO3）引起的腐蚀的被膜的前述基材的制造方法和使用了该基材的排烟脱硝催化剂的制造方法。
背景技术
将氨或尿素用于还原剂并用氧化钛系催化剂对氮氧化物进行无害化的所谓排烟脱硝装置以锅炉废气的处理为中心，在世界中广泛地使用。其催化剂形状有在金属或陶瓷制的网状物负载催化剂而制成板状的形状、将催化剂成分形成为蜂窝状的形状、粒状等，但在排烟脱硝的领域中，存在前两者将市场平分的状况。
对于用于该板状催化剂的基材，使用不锈钢（SUS），一般进行将其带板进行金属板网加工为网状而使用。作为不锈钢，具体地，铁素体系不锈钢板（SUS430）和奥氏体系不锈钢板（SUS304）等根据用途来区分使用。
发明内容
发明要解决的课题
对于上述现有技术，作为废气脱硝用催化剂的基材，价格高的SUS304在腐蚀显著的用途中使用，而且SUS430在比较平稳的腐蚀环境中使用的用途中使用等，实现了区分使用，但近年来，以稀土金属为首的金属材料的需求高涨，与其相伴，SUS材高涨，上述的区分使用变得困难。特别是SUS304容易受金属材料的高涨的影响，存在对催化剂价格的影响大的问题。另一方面，在美国，以高S碳为燃料的锅炉多，废气中的硫氧化物（SO3）达到50-100ppm也不少，产生了不能忽视用于废气脱硝用的催化剂的SUS430基材的腐蚀的情形。
本发明要解决的课题在于，鉴于上述状况，提供废气脱硝催化剂用金属基材，其能够提高价格低、容易稳定供给的SUS430基材的耐腐蚀性，能够与SUS304同样地不会腐蚀地使用。
用于解决课题的手段
为了实现上述课题，本申请请求专利保护的发明如下所述。
1．废气脱硝催化剂用金属基材的制造方法，其特征在于，对于对铁素体系不锈钢带状钢板进行了金属板网加工的带状金属板网基材，连续进行下述工序：（1）对附着于该基材的加工油进行脱脂的工序、（2）使基材潜入含磷酸和表面活性剂的溶液内而负载该溶液的工序、（3）对剩余的前述溶液进行除液的工序和（4）对负载有前述溶液的基材进行干燥和加热而使磷酸与基材反应的工序，从而在前述基材表面形成耐腐蚀性的磷酸化合物被膜。
2．废气脱硝催化剂用金属基材的制造方法，其特征在于，对于对铁素体系不锈钢带状钢板进行了金属板网加工的带状金属板网基材，（1）进行了对附着于该基材的加工油进行脱脂的工序后，（2）将该基材卷取为卷状，（3）将得到的卷材浸渍于含磷酸和表面活性剂的溶液而负载溶液，（4）通过吹气或离心力对前述溶液进行除液，（5）接下来仍以卷状进行干燥、加热，从而在该基材表面形成由磷酸与基材的反应产生的耐腐蚀性被膜。
3.上述1或2所述的方法，其中，前述铁素体系不锈钢带状钢板为SUS430不锈钢带状钢板。
4.上述1～3的任一项所述的方法，其中，前述加热的温度为300℃以上。
5.上述1～4的任一项所述的方法，其中，前述耐腐蚀性的磷酸化合物被膜的厚度为1μm以上。
6.排烟脱硝催化剂的制造方法，其特征在于，在采用上述1～4的任一项所述的方法得到的基材上放置以氧化钛为主成分的催化剂成分的糊剂，在上下一对的辊间通过，由此以催化剂糊剂将前述金属板网基材的开口部和表面填埋的方式涂布后，干燥、烧成。
如果将铁素体系不锈钢板（SUS430）制金属板网用于催化剂基材的催化剂用于SO3浓度高的废气的处理，则废气中的SO3与SUS430如下式所示反应，将基材表面慢慢地氧化。该氧化铁的一部分与废气中的SOX反应而形成硫酸盐，在装置停止时等湿润环境下潮解并移动到催化剂成分中，使催化剂的SO2氧化活性上升。
Fe＋SO3→FeO＋SO2（1式）
本发明人为了防止SUS430的SO3引起的上述氧化腐蚀，对于采用粒子状的稳定氧化物的涂布的被膜形成、SUS表面的采用磷酸的钝化膜的形成等进行了研究，但尚未达到防止气体状的SO3与金属的直接反应。推测这是因为，被膜为多孔质，未能完全地防止SO3分子的扩散，或者对于防止与SO3的反应，膜的厚度过薄。因此，对于能够防止SO3的扩散的、致密且厚、与金属的密合性优异的被膜的形成方法进行了深入研究，结果完成了本发明方法。
本发明方法的处理并不是一般所说的形成在金属表面形成的吸附了磷酸离子的薄的钝化膜，而是要使基材金属的0.1-几%与磷酸反应、在基材表面形成足以防止气体的扩散、致密且厚的磷酸铁或磷酸铬的层。具体地，将进行了金属板网加工的SUS430基材浸入含磷酸和表面活性剂的水溶液中后，采用吹气等将液体除去，在基材表面形成溶液的液膜后，边通气边干燥后，优选在300℃以上的温度下进行热处理。
这样，利用表面活性剂的作用，即使在干燥过程中液膜也得到保持，在金属表面形成磷酸的被膜。如果将该被膜进一步加热，超过300℃，则成为反应性极高的强磷酸，与SUS430的Fe或Cr反应，形成对应的盐类的致密的被膜。由于使金属的0.1-几%与磷酸反应，因此其厚度为厚1μm以上，优选2μm～几μm，能够高效率地防止SO3气与金属的接触。
可称为本发明方法的发明点的方面在于以下方面：在水溶液的阶段，利用表面活性剂的作用，形成均一的液膜，在干燥过程中，向粘稠的磷酸、进而向粘稠的强磷酸过渡，原样地使强磷酸与SUS430材料反应，因此能够形成即使几μm大的膜厚也无裂纹、均一的磷酸盐的被膜。
发明的效果
如上所示，根据本发明方法，能够保护SUS430制催化剂基材免受SO3引起的腐蚀，其结果，能够将价格低的SUS430基材用作在SO3浓度高的腐蚀环境下使用的脱硝催化剂基材，能够实现适于使用了价格高涨严重的SUS304基材的用途的催化剂的成本降低。
附图说明
图1是表示用于实施本发明的配置了必要的最小限度的设备的催化剂基材的制造流程的说明图。
图2是表示本发明的另一实施例的催化剂基材的制造方法的说明图。
图3是表示由采用本发明方法处理过的金属板网基材制造催化剂基材的工艺的说明图。
具体实施方式
图1是表示用于实施本发明的配置了必要的最小限度的设备的催化剂基材的制造流程的说明图。
将厚0.1-0.3mm的SUS430带钢1用金属板网加工机2加工为具有数mm的开口径的金属板网3，接着输送到脱脂装置4，将加工油通过加热或洗涤而除去（脱脂）。将前述处理过的金属板网潜入含磷酸和表面活性剂的液体5中，接下来，采用吹气装置6喷射压缩空气，将剩余的溶液除去，在金属板网表面形成表面张力平衡的、均一的磷酸的液膜。然后，将金属板网输送到干燥·热处理炉7进行干燥，接着加热到300℃以上，经过从磷酸到强磷酸、进而强磷酸与金属的反应的过程，在表面形成了牢固的磷酸盐被膜后，作为卷材13卷取。图中，12表示夹辊。
含磷酸和表面活性剂的溶液5中的磷酸的浓度也因形成的膜的必要厚度而异，大于1且50重量%以下、优选1～20重量%容易产生好结果。
此外，使用的表面活性剂，优选选择即使在磷酸中这样的强酸性下也不失效力的非离子系的表面活性剂，优选使用例如烷基苯氧基聚乙二醇型非离子性表面活性剂（ロッシュ社制、商品名トリトンX-100）等通常在强酸性下使用的表面活性剂。对其添加量并无特别限定，通常优选0.01重量%以上、0.1重量%以下。如果小于0.01重量%，作为表面活性剂的作用不充分，如果过多，则容易起泡。再有，该实施例中，示出了依次进行各工序用带状的金属板网连续处理的实例，但由于工序的处理速度不同的情形或设置场所的关系，当然能够在工序间将带状板网切断，暂时卷取为卷状来保管或者移动。
图2是表示本发明的另一实施例的催化剂基材的制造方法的说明图。与图1的实施例不同，将进行了金属板网加工的产物卷取为卷状，将得到的金属板网的卷材如图2所示输送到脱脂装置4进行脱脂后，进行在磷酸和表面活性剂溶液5中的浸渍、采用吹气6等的除液后，用干燥·加热炉7进行热处理。该实施例中，与如图1的实施例那样将金属板网以带状进行处理的情形相比，具有卷绕成卷状进行处理、能够容易保管的优点。
图3是表示由采用本发明方法处理的金属板网基材制造催化剂基材的工艺的说明图。
将金属板网基材3与采用公知的方法得到的脱硝催化剂成分糊剂一起输送到涂布机8，通过上下1对的加压辊，从而以糊剂填埋板网网眼，并且将基材表面覆盖的方式进行涂布。得到的带状薄板催化剂，在成型机9中用模具层压时，赋予成为间隔物的波纹，然后用切断机10切断为矩形的部件，在工序11中将该部件层叠，组装到催化剂单元。得到的催化剂单元在通气干燥后，用烧成炉烧成，作为脱硝用催化剂使用。
实施例
以下使用具体例对本发明详细说明。
实施例1
使对厚0.16mm、宽500mm的铁素体系不锈钢板（SUS430）制钢板进行了金属板网加工的产物，用约1分钟通过保持在400℃的炉内，对加工油进行脱脂。
另外，在10%磷酸中添加作为表面活性剂的烷基苯氧基聚乙二醇型非离子性表面活性剂（ロッシュ社制、商品名トリトンX-100）以成为0.025重量%，准备处理溶液，使上述脱脂后的金属板网在其中浸渍30秒。经过30秒后，将金属板网取出，喷射压缩空气，将在金属板网的板网网眼间架桥的溶液和因自重而垂挂的溶液除去，然后在150℃下干燥，接下来放入保持在350℃的电炉中10分钟，进行加热处理，得到了在表面形成了磷酸化合物的被膜的金属板网。
实施例2
除了将实施例1中使用的磷酸溶液的浓度变为20重量%，而且将热处理温度变为450℃以外，与实施例1同样地处理，得到了金属板网基材。
实施例3、4
将氧化钛和钼酸铵、偏钒酸铵以原子比计按Ti：Mo：V＝93.5：5：1.5的比例混合，加入水、硅溶胶、二氧化硅系陶瓷纤维，用捏合机充分混炼，得到了催化剂糊剂。在将本催化剂糊剂放置在实施例1和2的基材上的状态下使其通过一对加压辊，将催化剂糊剂压接涂布于基材的网眼间和表面。将其在150℃下干燥1小时后，在500℃下烧成2小时，得到了板状催化剂（涂布量700g/m2）。
比较例1
原样使用实施例1中使用的脱脂处理后的SUS430制金属板网基材。
比较例2
除了在实施例1中不使用表面活性剂以外，其他同样地进行被膜形成，制备金属板网基材。
比较例3
除了将实施例1的加热处理温度350℃变为250℃以外，与实施例1同样地制备金属板网基材。
比较例4～6
使用比较例1～3的基材，采用与实施例3和4同样的方法制备涂布了催化剂的催化剂。
试验例1
对于实施例1和2、比较例1和2中得到的金属板网基材，测定被膜形成处理引起的基材的重量增加量。此外，将100mm见方的上述基材用100ml的水洗涤，考察这前后的重量变化。除此之外，采用电子显微镜观察被膜的状态和磷（P）的分布状态。
由得到的与被膜形成相伴的重量增加量计算被膜的密度为2g/cm3时的膜厚，示于表1，同时将采用电子显微镜得到的被膜的状态和P的分布状态的观察结果一并示出。
由表1的结果可知，采用本发明方法处理的金属板网基材形成了计算为1.1～2.6μm的均一且无裂纹的磷化合物的被膜。此外，将实施例1与比较例2和3的结果进行比较可知，（1）表面活性剂没有共存的比较例2中，未能形成厚且均一的被膜，而且（2）热处理温度低的比较例3中，用水将被膜溶解除去。由这些可知，本发明的处理方法是能够在金属板网基材形成厚、均一且耐水性高的磷化合物的被膜的优异的方法。
实验例2
将实施例3和4、比较例4～6的催化剂使得以按硫酸铝计为5重量%的方式浸渍作为SO3的发生源的具有15%的游离硫酸根的硫酸铝的水溶液，然后在150℃下干燥。将得到的催化剂分别放入带盖的磁制坩埚中，实施了在450℃下保持300小时的加速腐蚀试验。为了掌握浸渍的硫酸铝慢慢热分解、生成的SO3腐蚀催化剂基板而生成的氧化铁的量，从上述劣化试验前后的板状催化剂将催化剂成分剥离，只将催化剂基板用加热的15%柠檬酸铵溶液处理。对此时溶出的Fe离子进行定量，由试验前后的定量值的变化计算因腐蚀而生成的氧化铁量（Fe2O3换算量）。
将得到的结果示于表2。如从表2中可知那样，对于使用了表1中没有形成不溶性的磷酸化合物的被膜的基材的比较例4～6的催化剂，腐蚀引起的氧化物的生成量显著地高，对于使用了本发明的基材的实施例3和4的催化剂，氧化铁的生成量极小。
[表1]
[表2]
| 区分 | 腐蚀量（g/m2） |
| 实施例3 | 0.7 |
| 实施例4 | 0.5 |
| 比较例4 | 3.6 |
| 比较例5 | 2.6 |
| 比较例6 | 3.1 |
附图标记的说明
1··SUS430带板、2··金属板网加工机、3··金属板网、4··脱脂装置、5··磷酸＋表面活性剂溶液、6··吹气装置、7··干燥·热处理炉、8··涂布机、9··成型机、10··切断机、11··层叠工序、12··夹辊、13··辊。
Claims (6)
1.废气脱硝催化剂用金属基材的制造方法，其特征在于，对于对铁素体系不锈钢带状钢板进行了金属板网加工的带状金属板网基材，连续进行下述工序：（1）对附着于该基材的加工油进行脱脂的工序、（2）使基材潜入含磷酸和表面活性剂的溶液内而负载该溶液的工序、（3）对剩余的前述溶液进行除液的工序和（4）对负载有前述溶液的基材进行干燥和加热而使磷酸与基材反应的工序，从而在前述基材表面形成耐腐蚀性的磷酸化合物被膜。
2.废气脱硝催化剂用金属基材的制造方法，其特征在于，对于对铁素体系不锈钢带状钢板进行了金属板网加工的带状金属板网基材，（1）进行了对附着于该基材的加工油进行脱脂的工序后，（2）将该基材卷取为卷状，（3）将得到的卷材浸渍于含磷酸和表面活性剂的溶液而负载溶液，（4）通过吹气或离心力对前述溶液进行除液，（5）接下来仍以卷状进行干燥、加热，从而在该基材表面形成由磷酸与基材的反应产生的耐腐蚀性被膜。
3.权利要求1或2所述的方法，其中，前述铁素体系不锈钢带状钢板为SUS430不锈钢带状钢板。
4.权利要求1～3的任一项所述的方法，其中，前述加热的温度为300℃以上。
5.权利要求1～4的任一项所述的方法，其中，前述耐腐蚀性的磷酸化合物被膜的厚度为1μm以上。
6.排烟脱硝催化剂的制造方法，其特征在于，在采用权利要求1-4的任一项所述的方法得到的基材上放置以氧化钛为主成分的催化剂成分的糊剂，在上下一对的辊间通过，由此以催化剂糊剂将前述金属板网基材的开口部和表面填埋的方式涂布后，干燥、烧成。
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| CN1565742A (zh) * | 2003-06-16 | 2005-01-19 | 浙江大学 | 不锈钢阳极氧化膜负载贵金属催化剂及制备方法 |
| CN1970147A (zh) * | 2005-11-22 | 2007-05-30 | 李毅 | 不锈钢酸洗液催化剂及其制备方法 |
| CN101028605A (zh) * | 2007-03-27 | 2007-09-05 | 天津大学 | 化学镀制备沸石分子筛膜负载贵金属催化剂的方法 |
| CN101274282A (zh) * | 2008-05-13 | 2008-10-01 | 浙江大学 | 不锈钢丝网阳极氧化膜负载稀土金属-贵金属催化剂的制备方法 |
| CN101284240A (zh) * | 2008-06-03 | 2008-10-15 | 浙江大学 | 一种钇-钯不锈钢丝网催化剂的制备方法 |
| CN101444741A (zh) * | 2009-01-04 | 2009-06-03 | 上海大学 | 不锈钢载体催化剂的制备方法和涂敷工艺 |
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| US4018706A (en) * | 1975-07-21 | 1977-04-19 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalysts for purifying exhaust and waste gases |
| JPS59335A (ja) * | 1982-06-25 | 1984-01-05 | Babcock Hitachi Kk | 耐摩耗性触媒の製造法 |
| JPS6486975A (en) * | 1987-09-29 | 1989-03-31 | Permelec Electrode Ltd | Preparation of calcium phosphate compound coated composite material |
| JPH04193962A (ja) * | 1990-11-27 | 1992-07-14 | Sumitomo Metal Ind Ltd | ステンレス鋼の表面処理方法 |
| US5267390A (en) * | 1991-04-15 | 1993-12-07 | Yang Duck J | Organic vapor deposition process for corrosion protection of prestamped metal substrates |
| JPH08117614A (ja) * | 1994-10-20 | 1996-05-14 | Matsushita Electric Ind Co Ltd | 触媒体およびその製造方法 |
| DE19915681A1 (de) * | 1999-04-07 | 2000-10-12 | Basf Ag | Verfahren zur Herstellung von Platinmetall-Katalysatoren |
| DZ3395A1 (fr) * | 2000-07-25 | 2002-01-31 | Shell Int Research | Reacteur comprenant un lit a garnissage de catalyseur ou de precurseur de catalyseur et son utilisation |
| JP4193962B2 (ja) | 2000-10-31 | 2008-12-10 | 独立行政法人産業技術総合研究所 | 太陽電池用基板および薄膜太陽電池 |
| DE102005023605A1 (de) * | 2005-05-18 | 2006-11-23 | Basf Ag | Katalysatoren und Verfahren zur Oxidation von Ammoniak |
| JP5615058B2 (ja) * | 2010-06-29 | 2014-10-29 | バブコック日立株式会社 | 排ガス脱硝触媒用金属基材の製造方法 |
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| CN1565742A (zh) * | 2003-06-16 | 2005-01-19 | 浙江大学 | 不锈钢阳极氧化膜负载贵金属催化剂及制备方法 |
| CN1970147A (zh) * | 2005-11-22 | 2007-05-30 | 李毅 | 不锈钢酸洗液催化剂及其制备方法 |
| CN101028605A (zh) * | 2007-03-27 | 2007-09-05 | 天津大学 | 化学镀制备沸石分子筛膜负载贵金属催化剂的方法 |
| CN101274282A (zh) * | 2008-05-13 | 2008-10-01 | 浙江大学 | 不锈钢丝网阳极氧化膜负载稀土金属-贵金属催化剂的制备方法 |
| CN101284240A (zh) * | 2008-06-03 | 2008-10-15 | 浙江大学 | 一种钇-钯不锈钢丝网催化剂的制备方法 |
| CN101444741A (zh) * | 2009-01-04 | 2009-06-03 | 上海大学 | 不锈钢载体催化剂的制备方法和涂敷工艺 |
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| JP2012011272A (ja) | 2012-01-19 |
| US20140228208A1 (en) | 2014-08-14 |
| KR20130089170A (ko) | 2013-08-09 |
| EP2589433A1 (en) | 2013-05-08 |
| JP5615058B2 (ja) | 2014-10-29 |
| CN102985179B (zh) | 2014-11-05 |
| EP2589433A4 (en) | 2014-08-27 |
| US9044736B2 (en) | 2015-06-02 |
| TWI502100B (zh) | 2015-10-01 |
| TW201213610A (en) | 2012-04-01 |
| KR101597868B1 (ko) | 2016-02-25 |
| WO2012002375A1 (ja) | 2012-01-05 |
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