CN105765190A - 氧化催化剂、用于制备其的方法和包括其的用于废气净化的过滤器 - Google Patents
氧化催化剂、用于制备其的方法和包括其的用于废气净化的过滤器 Download PDFInfo
- Publication number
- CN105765190A CN105765190A CN201480063089.4A CN201480063089A CN105765190A CN 105765190 A CN105765190 A CN 105765190A CN 201480063089 A CN201480063089 A CN 201480063089A CN 105765190 A CN105765190 A CN 105765190A
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- Prior art keywords
- oxidation catalyst
- amorphous metallic
- oxidation
- metallic alloy
- metal
- Prior art date
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 156
- 230000003647 oxidation Effects 0.000 title claims abstract description 152
- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000000746 purification Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 48
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 67
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000002912 waste gas Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000005300 metallic glass Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000007781 pre-processing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
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- 238000002485 combustion reaction Methods 0.000 description 3
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 229910052703 rhodium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 210000004556 brain Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
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Abstract
本发明涉及一种氧化催化剂、用于制备其的方法和包括其的用于废气净化的过滤器,更具体地,涉及这样一种氧化催化剂、用于制备其的方法和包括其的用于废气净化的过滤器,所述氧化催化剂通过包括非晶金属合金粉末而形成,从而能够以低成本制备、当施用到用于废气净化的过滤器时能够提高对废气的净化效率并且对于具有安装在其中的用于废气净化的过滤器的废气净化器的操作来说获得可靠性改善。为此,本发明提供了一种氧化催化剂、制备其的方法和包括其的用于废气净化的过滤器,所述氧化催化剂的特性在于涂覆到用于废气净化的过滤器的载体表面上并通过包括非晶金属合金粉末而形成。
Description
技术领域
本公开涉及一种氧化催化剂、制备其的方法和包括其的废气净化过滤器。更具体地,本公开涉及一种由于其组合物包括非晶金属合金粉末而能够以低成本制备、在施用到废气净化过滤器时能够改善废气净化的效率并且能够有助于改善其中设置废气净化过滤器的废气净化器的操作的可靠性的氧化催化剂。另外,本公开涉及一种制备氧化催化剂的方法和包括氧化催化剂的废气净化过滤器。
背景技术
一般而言,通过各种类型的设备(诸如电厂、炼铁厂和焚烧炉)中的各种燃烧反应器的操作排放的废气会由于低温、湿气含量、不足量的氧等而未完全燃烧。作为通过不完全燃烧排放到空气的最常见气体的一氧化碳(CO)在被吸入人呼吸道中时对人脑的供氧具有严重的影响。因此,用于减少从热电厂、炼铁厂和用于运输的装置(例如车辆)排放的废气的CO浓度的强制法规将生效。
因此,已经开发了用于将有害组分(诸如一氧化碳和烃)转换成无害组分的氧化催化剂体系。图1示出催化转化器作为这样的氧化催化剂体系的示例的催化转化器。催化转化器具有包括基底和载体的多孔陶瓷过滤器的表面用催化剂颗粒涂覆的结构。催化转化器的催化剂允许引入到催化转化器中的一氧化碳或烃与供应到催化转化器的氧反应。通过该反应,一氧化碳或烃转化成可以随后从催化转化器排放的二氧化碳或水。
这里,具有优异的反应性和稳定性的元素(诸如铂(Pt)或铑(Rh))通常用于涂覆多孔陶瓷过滤器的表面的催化剂。然而,Pt和Rh是具有有限储量的稀土金属,而其价格最近由于其增加的需求而呈现出快速增长。这导致废气净化过滤器的制造成本的增加。另外,当长时间段地暴露于温度范围为500℃至600℃的废气时,Pt会由于颗粒的生长或脱落而不利地劣化,使得废气净化的效率降低。
[现有技术文件]
第10-1251499号韩国专利(2013.4.1.)
发明内容
技术问题
因此,考虑到本领域中发生的上述问题,已经做出本发明,并且本发明意图提出由于其组合物包括非晶金属合金粉末而能够以低成本制备、当施用到废气净化过滤器时能够改善废气净化的效率并能够有助于改善其中设置废气净化过滤器的废气净化器的操作的可靠性的氧化催化剂。本公开还提出制备氧化催化剂的方法和包括氧化催化剂的废气净化过滤器。
技术方案
根据一方面,本公开提供了涂覆废气净化过滤器的载体的表面的氧化催化剂,其中,氧化催化剂由非晶金属合金粉末形成。
这里,非晶金属合金粉末可以是包括从由Fe、Ni、Mn、Co、Zr和Pt组成的组中选择的至少一种元素和从由B、Y、Ti、P、Pd、Be、Si、C、Ag、Na、Mg、Ga和Al组成的组中选择的至少两种元素的混合物。
另外,非晶金属合金粉末的颗粒尺寸可以在0.1μm至10μm的范围。
非晶金属合金粉末的表面粗糙度值可以在1nm至10nm的范围。
本公开还提供了制备涂覆废气净化过滤器的载体的表面的氧化催化剂的方法。该方法可以包括:将金属和母合金熔融的熔融步骤;通过将包括金属和母合金的熔融金属合金快速冷却来生产非晶金属合金的快速冷却步骤;以及将非晶金属合金转换成粉末的粉末化步骤。
在熔融步骤中,可以使用从由Fe、Ni、Mn、Co、Zr和Pt组成的组中选择的至少一种元素和从由B、Y、Ti、P、Pd、Be、Si、C、Ag、Na、Mg、Ga和Al组成的组中选择的至少两种元素作为金属和母合金。
在熔融步骤中,可以使用Fe、B、Y、Ti和Pt作为金属和母合金。
在熔融步骤中,可以以至少50原子%的Fe、10原子%至30原子%的B、5原子%至20原子%的Y和0原子%至10原子%的Ti+Pt的比使用Fe、B、Y、Ti和Pt作为金属和母合金。
在快速冷却步骤中,熔融金属合金可以以100℃/s至1,000,000℃/s的范围的冷却速率冷却。
另外,粉末化步骤可以包括在真空雾化(vacuumatomization)或熔体纺丝(meltspinning)之后的粉碎。
该方法还可以包括在粉末化步骤之后增加非晶金属合金的表面粗糙度值的步骤。
另外,该方法还可以包括在氧气氛中在从300℃至600℃的范围的温度下氧化非晶金属合金粉末的氧化步骤。
这里,在氧化步骤之后,由非晶金属合金粉末形成的氧化催化剂具有在150℃下将95%或更多的CO转换成CO2的性质,氧化催化剂不会与NO反应。
在氧化步骤之后,由非晶金属合金粉末形成的氧化催化剂具有在300℃下用于75%或更多的NH3的氧化性质,氧化催化剂在NH3的氧化期间可以不产生NO2副产物。
在氧化步骤中,随着热处理温度增加,非晶金属合金的表面结构可以从FeO结构(其中,非晶金属合金中Fe的氧化程度是+2)变为Fe2O3结构(其中,非晶金属合金中Fe的氧化程度是+3)。
另外,本公开提供了一种废气净化过滤器,所述废气净化过滤器包括:如上面描述的氧化催化剂;以及载体,其表面涂覆有氧化催化剂。
有益效果
根据本公开,使用由具有优异的耐久性的非晶金属合金粉末制备的氧化催化剂代替由诸如Pt或Rh的贵金属形成的现有技术中的催化剂。由此,能够显著地降低现有技术的制造成本。当氧化催化剂施用到废气净化过滤器时,能够改善废气净化的效率,从而有助于改善废气净化器的操作的可靠性。
附图说明
图1是示意性地示出典型的催化转化器的结构视图;
图2是示出结晶金属的原子结构的概念视图;
图3是示出非晶金属的原子结构的概念视图;
图4是顺序地示出根据示例性实施例的制备氧化催化剂的方法的工艺步骤的流程图;
图5是示出通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂的表面形状的SEM显微图;
图6是示出通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂的XRD图;
图7是示出对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的CO氧化测试的结果的曲线图;
图8是示出在预处理之后对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的CO氧化测试的结果的曲线图;
图9是示出对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的NO氧化测试结果的曲线图;
图10是示出对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的NO-TPD测试结果的曲线图;
图11是示出在预处理之后对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的NH3氧化测试结果的曲线图;
图12是示出在预处理之后对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的NH3氧化测试期间的NO2浓度测量的曲线图;
图13是示出对通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂执行的基于氧化的XPS变化的曲线图;
图14是通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂的TEM照片;以及
图15是示出氧化之前和氧化之后通过根据示例性实施例的制备氧化催化剂的方法制备的氧化催化剂的XRD图。
具体实施方式
在下文中,将结合附图详细地参照根据本公开的氧化催化剂、制备其的方法和包括其的废气净化过滤器,在附图中示出了本公开的示例性实施例。
另外,在本发明的描述中,在本发明的主题因包含已知功能和组件的详细描述而被导致不清楚的情况下,将省略已知功能和组件的详细描述。
根据示例性实施例的氧化催化剂是涂覆设置在废气净化器(其设置在电厂、焚烧炉、船舶(vessel)等中)中的废气净化过滤器的载体的表面的催化剂,以参与或促进用于将废气中包含的有害组分(诸如CO或NH3)转化成无害组分的化学反应。根据本实施例的氧化催化剂包含非晶金属合金粉末。
与参照图2和图3的有结晶金属的非晶金属相比,非晶金属以具有非常高的表面能和活性为特征,因为其表面的原子结构是高度无序的并且形成原子键之间表示缺陷的多个自由键。另外,非晶金属由于物理、化学和结构因素可以比结晶金属具有更高的抗腐蚀性和更高的机械强度。
因此,根据本实施例的氧化催化剂在非晶金属的这些特性的基础上被作为用于净化废气的催化剂。当由非晶金属合金粉末形成根据本实施例的氧化催化剂用来净化废气时,与使用贵金属催化剂的现有技术工艺相比,能够改善废气净化的效率。另外,氧化催化剂可以以低成本制备,使得具有设置为废气净化催化剂的氧化催化剂的废气净化过滤器可以以显著低的成本来制备。
另外,由于非晶金属合金由于具有从500℃至600℃的范围的温度的废气既不凝缩也不结晶,因此非晶金属合金具有优异的耐久性。因此,由非晶金属合金形成的氧化催化剂在长时间段地暴露于废气时不从废气净化过滤器的载体脱落,从而有助于改善包括设置氧化催化剂的废气净化过滤器的废气净化器的操作的可靠性。
如上面描述的氧化催化剂可以由非晶金属合金粉末形成,所述非晶金属合金粉末通过混合从由Pt、Ni、Fe、Co和Zr组成的组中选择的至少一种和从由B、P、Pd、Be、Si、C、Ag、Na、Mg、Ga、Y、Ti和Al组成的组中选择的至少两种而产生。即,根据本实施例的氧化催化剂的组合物可以包括三种或更多种元素。
另外,氧化催化剂的非晶金属合金粉末的颗粒尺寸可以为0.1μm至10μm的范围。此外,优选的是,氧化催化剂的非晶金属合金粉末的表面粗糙度为1nm至10nm的范围,使得氧化催化剂具有用于催化剂的最佳比表面积。
在下文中,将参考根据示例性实施例的制备氧化催化剂的方法。
如图4中所示,根据本实施例制备氧化催化剂的方法是制备涂覆设置在废气净化器(设置在电厂、焚烧炉、船舶等中)中的废气净化过滤器的载体的表面的氧化催化剂并包括熔融步骤S1、快速冷却步骤S2和粉末化步骤S3的方法。
首先,熔融步骤S1是将金属和母合金熔融的步骤。即,在熔融步骤S1中,通过将金属和母合金插入到坩埚中并随后加热金属和母合金来制备熔融的液态金属合金。在熔融步骤S1中,可以使用从由Fe、Ni、Mn、Co、Zr和Pt组成的组中选择的至少一种元素和从由B、Y、Ti、P、Pd、Be、Si、C、Ag、Na、Mg、Ga和Al组成的组中选择的至少两种元素作为金属和母合金。例如,在熔融步骤S1中,可以选择Fe、B、Y、Ti和Pt作为金属和母合金。在此情况下,在熔融步骤S1中,金属与母合金的含量比可以控制为至少50原子%的Fe、10原子%至30原子%的B、5原子%至20原子%的Y和0原子%至10原子%的Ti+Pt。
随后的快速冷却步骤S2是将熔融的金属合金快速冷却的步骤。即,快速冷却步骤S2通过快速冷却熔融的金属合金而产生非晶金属合金。就这点而言,在快速冷却步骤S2中,熔融的金属合金可以以100℃/s至1,000,000℃/s范围的冷却速率冷却。当如上面描述快速冷却熔融的金属合金时,熔融的金属合金以像玻璃一样的无序原子布置而凝固,从而形成非晶金属合金。
最后的粉末化步骤S3是将非晶金属合金转换成粉末的步骤。粉末化步骤S3可以是真空雾化或熔体纺丝。即,粉末化步骤S3可以通过真空雾化将非晶金属合金转换成其颗粒尺寸为10μm至50μm的范围的粗粉,然后通过另外的机械研磨将粗粉转换成其颗粒尺寸为0.1μm至10μm的范围的细粉。另外,粉末化步骤S3可以通过熔体纺丝将非晶金属合金转换成非晶金属带,然后通过机械研磨将非晶金属带转换成粉末。
当完成如上面描述的粉末化步骤S3时,制备了由非晶金属合金粉末形成的氧化催化剂。
根据本实施例的制备氧化催化剂的方法还可以包括在粉末化步骤S3之后增加非晶金属合金粉末的表面粗糙度的步骤。这里,为了通过获得更大的比表面积而改善氧化催化剂的性质和通过获得较粗糙的表面增加废气净化过滤器对陶瓷载体的兼容性和结合力,增加非晶金属合金粉末的表面粗糙度。该步骤可以是通过使用流体的机械粉碎技术在非晶金属合金粉末的表面上形成纳米级结构的工艺。通过该工艺,可以制备具有最佳比表面积的金属合金粉末,其表面粗糙度水平为从1nm至10nm的范围。
在下文中,将结合图5至图15参考对通过根据本实施例的制备氧化催化剂的方法制备的氧化催化剂的特性执行的测试的结果。
图5是示出通过根据本实施例的制备氧化催化剂的方法制备的氧化催化剂的表面形状的扫描电子显微镜(SEM)显微图。在本实施例中,制备了由(Fe72B22Y6)Ti2和((Fe72B22Y6)Ti2)Pt2形成的氧化催化剂样品。两种样品都通过重复实验的工艺制备为具有再现性。
使用电弧熔化器均匀地制备其组合物包括预定比率的上面描述的元素的母合金。通过Spex研磨或球磨粉碎将熔体纺丝机制造的非晶带转换成具有如图5中示出的表面形状和颗粒尺寸的粉末。通过对关于表面形状和平均颗粒尺寸的SEM显微图的分析,认识到,制造的粉末的颗粒尺寸在5μm至10μm的范围。
图6示出意图检查由根据本实施例制备的非晶金属合金粉末形成的氧化催化剂的原子结构的XRD分析的结果,可以认识到,由于制造的带不具有XRD峰,但是具有表示均匀的非晶结构的宽XRD图案,因此非晶金属带通过如期望的上面描述的方法来制备。由于粉末样品具有与Spex研磨之后相同的图案,因此,可以认识到,在研磨期间没有发生结晶。
图7是示出为了检查由根据本实施例制备的非晶金属合金形成的氧化催化剂的性质所测量的CO氧化性质的曲线图。可以从图7认识是,Fe基非晶金属粉末在250℃或更高的温度下随着两个样品组合物的CO转化比达到70%或更高而明显地具有CO氧化催化活性。另外,可以认识到,包括2原子%的Pt元素的样品组合物具有如期望的更高的氧化催化性质。如曲线图中表示的,重复两次的实验示出一致的测试结果,从而使测试结果可靠。
在图7中,在氧化催化剂由非晶金属合金粉末形成之后立即执行CO氧化测试。然而,为了改善氧化催化剂的性质,通常执行以几百度(300℃至700℃)氧化或还原样品的预处理。预处理可以调整由非晶金属合金粉末形成的氧化催化剂的氧化态并优化用于材料的催化活性。
图8示出预处理(高温氧化)之后制备的非晶金属合金粉末样品的CO氧化性质的变化。如曲线图中表示的,当在以400℃、500℃和600℃对样品执行的高温氧化之后执行CO氧化时,所有的样品具有改善的氧化性质。具体地,在以600℃氧化的情况下,CO转化比比150℃的相对低的温度下的95%的转化比高。该转化比超过了作为可商业获得的催化剂的Pt的转化比。
图9是示出意图检查如上面描述所制备的由非晶金属合金形成的氧化催化剂样品是否对NO氧化具有影响的NO氧化测试结果的曲线图。该测试被设计为测量在NO流经样品之后NO2的浓度的变化。然而,如图9中的结果所示,确定在宽温度范围内注入的NO被排放而未转化成NO2。
因此,为了确定所制备的氧化催化剂样品不同于优异的CO氧化性质而对NO氧化不具有影响的原因,执行了NO程序升温脱附(NO-TPD)测试,结果示出在图10中。NO-TPD意图检查用于NO分子吸附的性质。首先,样品在NO中是饱和的,然后,分析NO的脱附信号,同时升高温度,由此计算在样品中吸附的NO的量。
从图10的结果中可以认识到,由于在预处理之前和预处理之后基本上没有检测到NO脱附的量,因此根据本实施例制备的氧化催化剂完全不吸附NO,同时现有技术中开发的NO氧化催化剂吸附显著量的NO,因此,可以明显地测量NO脱附的量。由于氧化催化剂样品基本上没有吸附NO的量,因此,氧化催化剂具有选择性的CO氧化性能。
根据本实施例制备的氧化催化剂的选择性的CO氧化性质适用于各种重要的工业领域。具体地,目前,为了氧化来自电厂或焚烧炉的废气中的CO,一般使用可商业获得的Pt催化剂。该工艺的副作用是作为副反应发生的NO2生成。与无色无味的NO不同,当在空气中仅包含15ppm的NO2时,NO2形成具有气味的可察觉到的黄烟。为了克服该问题,需要诸如输入乙醇的附加工艺。相比之下,根据本实施例制备的氧化催化剂对于CO是完全选择性的,因此,不引起诸如NO2生成的副作用。因此,不需要诸如输入乙醇的附加工艺。
图11是示出使用根据本实施例制备的氧化催化剂样品对氨(NH3)执行的氧化测试结果的曲线图。从曲线图的结果可以认识到,在400℃和600℃下预处理的样品在300℃的温度范围中都具有80%或更高的氨转化比。
图12是示出意图确定在通过图11中示出的氨氧化测试转换的气体中是否发生NO2副反应的NO2浓度测量的曲线图。该曲线图指示出,NO2浓度为0ppm,即,不产生NO2。如从NO-TPD测试认识到的,可以解释为在氨氧化期间产生的NO分子未被吸附到非晶金属合金粉末的表面且因此未转化NO2的选择性氧化的结果。在处理由滑离(slip)导致的残余氨或处理在若干化学过程中作为副产物产生的氨的De-NOxSCR体系中发现了氨的选择性氧化的应用。当该体系使用根据本实施例制备的氧化催化剂时,可以识别氧化催化剂体系,而没有NO2的气味和黄色烟的问题。
图13示出与在根据本实施例的制备氧化催化剂的方法中粉末化之后的样品中以及在根据本实施例的制备氧化催化剂的方法中粉末化之后被氧化的样品中所包含的金属组分中的Fe有关的XPS数据。可以基于XPS数据测量元素的结合能水平并基于结合能水平预测期望的材料的表面的原子结构,从而确定金属的氧化态。如从图13中的曲线图认识到的,通过测量作为制备的氧化催化剂的主要元素的Fe的XPS峰,能够确定三种类型的铁氧化物(即,FeO(Fe氧化态:+2)、Fe2O3(+3)和Fe3O4(+8/3))中的峰的位置和强度。如从XPS结果曲线图所认识到的,在预处理之前的样品的情况下,FeO(其中,Fe的氧化程度为+2)具有最大的峰。在400℃下预处理之后,Fe2O3和Fe3O4的峰逐渐增大。具体地,该趋势在600℃下的预处理之后更突出。与CO氧化性质随着如在400℃和600℃的预处理中的预处理温度逐渐增大而更高的结果(图8)相比,可以总结出,催化性质将随着表面结构更接近于Fe2O3的表面结构而更高,其中,氧化程度由+2变为+3。
一般而言,诸如FeO和Fe2O3的金属氧化物具有规则的晶体结构。为了检查规则的结晶结构,图14示出的透射电子显微镜(TEM)测量的结果意图分析基于XPS数据确定的铁氧化物的表面的原子结构。如从XPS预期的,从TEM显微图观察到由表面氧化引起的初始非晶金属的非晶结构中的结晶部分。从快速傅里叶变换(FFT)图像可以认识到,由部分表面氧化引起的纳米结晶结构部分地分布,尽管未分布在整个表面上。
虽然根据本实施例制备的氧化催化剂的表面的特定部分由于氧化而结晶,但是由于形成氧化催化剂的非晶金属合金既没有因具有从500℃至600℃的范围的温度的废气而凝聚也未因其而结晶,因此氧化催化剂通常具有优异的耐久性。如图15中所示,在粉末化步骤之后和在继粉末化步骤之后的在600℃下的氧化预处理之后,通过XRD分析来测量非晶XRD图案。即,关于总体颗粒结构,可以认识到,在600℃下执行煅烧达四小时之后维持相同的结构而不结晶。因此,根据本实施例的由非晶金属合金粉末形成的氧化催化剂不受劣化、生长等的影响,因此,即使在已经长时间段地暴露于废气之后,也不从废气净化过滤器的载体的表面脱落。因此,氧化催化剂的性质优于现有技术的Pt和Rd催化剂的性质。
另外,根据本实施例制备的氧化催化剂应用到废气净化过滤器。具体地,废气净化过滤器可以包括其表面涂覆有根据本实施例制备的氧化催化剂的载体。废气净化过滤器可以通过下述步骤来制造:通过将由非晶金属合金粉末形成的氧化催化剂混合到溶剂中来形成浆料,以及通过将多孔载体浸入浆料中对多孔载体的表面涂覆氧化催化剂层。
为了制造废气净化过滤器,进行更详细地描述,首先,通过用水溶性溶剂、醇类溶剂或它们的混合物稀释氧化催化剂来形成浆料。在此情况下,优选的是,以从10wt%至50wt%的范围的溶剂的比添加氧化催化剂。
如上面描述的溶剂可以包括分散剂以改善氧化催化剂的分散性。为了实现基于空间位阻的分散性,分散剂可以包括诸如CTAB或DTAB的表面活性剂,或者为了实现电分散性,可以包括从NH4OH、NaCl和NH4Cl中选择的至少一种盐。
然后,通过将多孔载体浸入制备的浆料中在载体的表面上形成氧化催化剂层。这里,优选地是,氧化催化剂层的厚度被控制为从0.5μm至5μm的范围。
接着,通过在100℃至150℃范围的温度下加热在其表面上具有氧化催化剂层的多孔载体长达2小时来蒸发溶剂。然后通过在450℃至550℃的范围的温度下加热多孔载体来烧结氧化催化剂层,从而完成废气净化过滤器的制造。
已经参照附图给出了本公开的特定实施例的上述描述。它们并不意图是详尽的或意图将本公开限制为这里公开的精确形式,鉴于上述教导,对于本领域普通技术人员来说,明显地可以进行许多修改和变型。
因此,本公开的范围不意图限于上述的实施例,而是由其所附的权利要求和它们的等同物限定。
Claims (16)
1.一种氧化催化剂,所述氧化催化剂涂覆废气净化过滤器的载体的表面,并包括非晶金属合金粉末。
2.根据权利要求1所述的氧化催化剂,其中,非晶金属合金粉末包括包含从由Fe、Ni、Mn、Co、Zr和Pt组成的组中选择的至少一种元素和从由B、Y、Ti、P、Pd、Be、Si、C、Ag、Na、Mg、Ga和Al组成的组中选择的至少两种元素的混合物。
3.根据权利要求1所述的氧化催化剂,其中,非晶金属合金粉末的颗粒尺寸在0.1μm至10μm的范围。
4.根据权利要求1所述的氧化催化剂,其中,非晶金属合金粉末的表面粗糙度值在1nm至10nm的范围。
5.一种制备涂覆废气净化过滤器的载体的表面的氧化催化剂的方法,所述方法包括:
熔融步骤,将金属和母合金熔融,以产生包括金属和母合金的熔融金属合金;
快速冷却步骤,通过将熔融金属合金快速冷却来产生非晶金属合金;以及
粉末化步骤,将非晶金属合金转换成粉末。
6.根据权利要求5所述的方法,其中,在熔融步骤中,使用从由Fe、Ni、Mn、Co、Zr和Pt组成的组中选择的至少一种元素和从由B、Y、Ti、P、Pd、Be、Si、C、Ag、Na、Mg、Ga和Al组成的组中选择的至少两种元素作为金属和母合金。
7.根据权利要求6所述的方法,其中,在熔融步骤中,使用Fe、B、Y、Ti和Pt作为金属和母合金。
8.根据权利要求7所述的方法,其中,在熔融步骤中,以至少50原子%的Fe、10原子%至30原子%的B、5原子%至20原子%的Y和0原子%至10原子%的Ti+Pt的比使用Fe、B、Y、Ti和Pt作为金属和母合金。
9.根据权利要求5所述的方法,其中,在快速冷却步骤中,熔融金属合金以100℃/s至1,000,000℃/s的范围的冷却速率进行冷却。
10.根据权利要求5所述的方法,其中,粉末化步骤包括在真空雾化或熔体纺丝之后的粉碎。
11.根据权利要求5所述的方法,所述方法还包括在粉末化步骤之后增加非晶金属合金的表面粗糙度值的步骤。
12.根据权利要求5所述的方法,所述方法还包括在氧气氛中在从300℃至600℃的范围的温度下氧化非晶金属合金粉末的氧化步骤。
13.根据权利要求12所述的方法,其中,在氧化步骤之后,包括非晶金属合金粉末的氧化催化剂具有在150℃下将95%或更多的CO转换成CO2的性质,并且不与NO反应。
14.根据权利要求12所述的方法,其中,在氧化步骤之后,包括非晶金属合金粉末的氧化催化剂具有在300℃下用于75%或更多的NH3的氧化性质,并在NH3的氧化期间不产生NO2副产物。
15.根据权利要求12所述的方法,其中,在氧化步骤中,随着热处理温度增加,非晶金属合金的表面结构从非晶金属合金中的Fe的氧化程度为+2的FeO结构变为非晶金属合金中的Fe的氧化程度为+3的Fe2O3结构。
16.一种废气净化过滤器,所述废气净化过滤器包括:
如权利要求1至4中的任一项所述的氧化催化剂;以及
载体,其表面涂覆有所述氧化催化剂。
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JP2016538992A (ja) | 2016-12-15 |
KR20150059062A (ko) | 2015-05-29 |
US10046312B2 (en) | 2018-08-14 |
US20160288103A1 (en) | 2016-10-06 |
KR101555924B1 (ko) | 2015-09-30 |
CN105765190B (zh) | 2019-01-11 |
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