CN101757953B - 氨氧化催化剂 - Google Patents
氨氧化催化剂 Download PDFInfo
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- CN101757953B CN101757953B CN200910258426.6A CN200910258426A CN101757953B CN 101757953 B CN101757953 B CN 101757953B CN 200910258426 A CN200910258426 A CN 200910258426A CN 101757953 B CN101757953 B CN 101757953B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000006260 foam Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 230000001413 cellular effect Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 241001466460 Alveolata Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- -1 cobalt metal oxide Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- 229910017114 Fe—Ni—Al Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
- C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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Abstract
氨氧化催化剂单元，包括成对蜂窝型块体，所述块体具有内置于它们之间的气体渗透性材料层，该材料层的作用是径向混合气流，所述块体包含氨氧化催化剂，并且具有小于15cm的高度，并且内置层高度为3‑0.5cm。
Description
技术领域
本发明涉及一种由成对蜂窝型块体形成的氨氧化催化剂单元，所述块体包含氨氧化催化剂并且具有置于其间的泡沫材料层。
背景技术
多年来，用于氨氧化的催化剂是由铂或其与其它贵金属的合金的筛网(mesh)或丝网(gauze)形成的。
这些催化剂具有良好的活性和选择性，但其缺点是，该催化剂不仅非常昂贵，而且在氧化反应的高温下表现出明显的铂损失以及由此造成的短的催化剂寿命，其需要频繁地更换。
因此，希望提供这样的贵金属催化剂的替代品。
众所周知的是，金属例如锰、铁、镍、或尤其是钴金属的氧化物(通常与一种或多种稀土金属氧化物结合使用)表现出对氨氧化反应的活性。
CN-A-86/108985中描述了一种式La1-xCeCoO3的催化剂组成(其中X是从0到1的数字)，其具有钙钛矿型结构，在按小规模测试时具有良好的活性和选择性，在氨氧化反应通常所用的温度(800-1000℃)下工作时该活性和选择性降低。
US P4963521描述了一种废气催化剂，在一个实施方案中，该催化剂由这样的蜂窝堇青石形成，该蜂窝堇青石涂覆有与少量氧化锆和氧化铈混合的γ氧化铝的第一层和由氧化钴或铂、铑及钯形成的第二层。
没有提及该催化剂可用于将氨氧化。
US P5217939描述了一种氨氧化催化剂，该催化剂通过用氧化钴或者用贵金属涂覆网状泡沫陶瓷或金属基材获得。
通过将泡沫基材浸渍在钴或贵金属的羧酸盐溶液中，然后将基材从该溶液取出，并在260℃至800℃的温度下煅烧(在该温度下羧酸钴转化成氧化物，并且贵金属的羧酸盐还原成金属)，获得该涂层。
该泡沫陶瓷具有每线性英寸10-100个孔数目(4-40/cm)；在实施例中为30个孔。
氨到NO的转化率在使用涂覆Co氧化物的泡沫时为92-95％；使用涂有Pt的泡沫时为97-100％。
需要进一步的处理以将一氧化氮转化(NO转化为NO2)，然后将其转化为硝酸。
因此在硝酸的生产中需要更为高效和经济的催化剂。
US P5690900描述了用于产生相对较高的NO2收率的更为有效的催化剂。该催化剂由涂有至少3个层的多孔陶瓷(200-600胞孔/平方英寸，即14-24胞孔/线性英寸＝5-9胞孔/厘米)形成：第一层由氧化铝与较小比例的氧化铈和氧化锆形成，第二层为钴、锆和铈的氧化物，第三层为铂金属。
通过将多孔陶瓷体浸没在氧化铝、氧化锆和硝酸铈的悬浮液中，然后取出经浸渍的陶瓷结构体并在600℃至1000℃下煅烧，获得所述涂层。
所得表面积为80-120m2/g。
然后将如此涂覆的陶瓷浸渍在乙酸钴、硝酸铈及乙酸锆溶液中，将其从溶液中取出，并在600-1000℃下煅烧。
通过浸渍在草酸铂溶液中，并在600-1000℃下煅烧从前述处理的溶液中取出的结构体，获得最后涂层。
氨转化为NO/NO2的转化率为95-100％，并且NO/NO2比为75/25-60/40。
US 4820678描述了具有钙钛矿结构(ABO3)或尖晶石(A2BO4)结构的涂有催化剂的类蜂窝状合金带，其中的A包括稀土金属的阳离子，钙钛矿结构中的B选自锰、铜和镍阳离子，尖晶石结构中的B选自铁和镍。
该催化剂用于净化工业废气、来自汽车的废气和空气的净化。
通过在约0.05-0.12mm厚的Fe-Cr-Al或Fe-Ni-Al合金带上以间距约1.1-1.2mm进行穿孔以形成0.4×0.4mm的小孔，形成所述蜂窝状带。
发明内容
本发明的目的是提供氨氧化催化剂，其包含在蜂窝型结构中(其中，由于它们的管状结构，无径向气流混合发生，且因此没有令人满意的反应物转化率)，所述结构能够产生在活性和选择性方面较高的催化性能，以及与蜂窝状结构床体积和催化剂重量有关的高的比生产率。
本发明的氨氧化催化剂由一个或多个单元结构形成，每个单元结构由具有蜂窝型结构并包含催化剂材料的成对块体组成，所述块体在其之间内置有气体渗透性材料层，在其中获得反应物气流的径向混合。
该块体具有不大于15cm、优选不大于10、更优选不大于6cm并且大于2cm的高度。所述内置层的高度大于0.5cm，而不大于3cm，优选不大于2cm。
具有开口、随机连接的胞孔的泡沫材料可用于形成该内置层。
对于蜂窝型结构，其意味着由不相互连接的管形通孔所形成的结构。
如所示，在上述结构中，在第一蜂窝块体中，由于层流活塞式流在不相互连接的管形通孔中流动，没有发生径向混合，内置层起到的作用是彻底混合从该第一蜂窝块体出来的气流，因此允许在第二块体内获得较好的转化。
层流活塞式流在块体的管状通孔内流动有利于在与催化剂接触时维持恒定的反应物浓度，所述催化剂覆盖通孔壁。
蜂窝型块体的材料优选为陶瓷或金属；还可使用任何其它能够耐受氨氧化反应的高温的材料。例如，蜂窝型块体的材料可为ABO3型钙钛矿，其中的A是稀土元素或碱土元素或其混合物，B是过渡金属元素或其混合物。
胞孔的密度为3-10胞孔/cm；泡沫材料中孔的密度为4至20/cm。
商用蜂窝型块体可得自Emitech-Germany，商用泡沫来自Hi-TechCeramics-NY，USA。
优选泡沫α氧化铝和具有任意连接的开孔的网状泡沫。
还可由根据US P4820678制备的带材获得可用的蜂窝型合金块体。
任何类型的氨氧化催化剂可用于根据本发明的蜂窝型结构单元。最终的催化剂可通过以下任一项获得：
a)用活性元素涂覆惰性蜂窝整体结构
或者
b)将活性元素粉末挤压到蜂窝整体型结构上。
优选的催化剂包含钴、锰和稀土金属的混合氧化物，该混合氧化物具有以CoO、MnO和最低价态稀土氧化物的重量百分数表示的如下组成：20-45％CoO、50-60％MnO、0.5-20％稀土金属氧化物(优选La2O3及其与CeO2的混合物)。所述混合氧化物负载在多孔无机金属氧化物、优选γ氧化铝上。WO 2008-090450中描述了含有CuO而不是CoO的该类型的催化剂及其制备方法。
US P5217939和5690900以及WO 99/25650描述了其它可用催化剂的实例。其它实例为钙钛矿型催化剂(ABO3)和尖晶石型(AB2O4)。
该催化剂单元允许获得氨到NO的高转化率。
氧化反应条件为：温度为200℃-900℃，压力为1-12巴(绝对)，GHSV为8.000-140.000h-1。
该单元由于其特殊的结构而在回压方面提供了优点，并且因为现有工厂生产量可得到更重负荷而提高时空收率。
具体实施方式
实施例1
通过将块体浸没在包含研磨至1-10μm的γ氧化铝的浆液中来制备催化剂单元，该催化剂单元由三个类蜂窝状结构陶瓷块体单元形成，所述陶瓷块体分别具有5cm高度、62胞孔/cm2，并且包括两层分别为2cm厚的内置的泡沫α氧化铝，一个整体块与一个泡沫体相交替直至该5个结构体以层叠形式布置，所述γ氧化铝具有负载于其上的混合氧化物催化剂，该催化剂组成以CoO、MnO和La2O3的重量百分数表示为37.4％CoO、53.4％MnO和9.2％La2O3。所述负载催化剂还包含0.1-0.2wt％的量的Pt。所述的过渡金属氧化物负载在γ氧化铝上，其总量等于20％重量。所述浆液进一步包含去离子水并用乙酸使酸性达到pH4。
通过用硝酸镧(La(NO3)3)水溶液浸渍γ氧化铝来制备催化剂。
然后将该经浸渍的载体在110℃干燥、在600℃煅烧，然后将其用硝酸锰(Mn(NO3)2)、硝酸钴(Co(NO3)2)和Pt(NH3)4Cl2的水溶液浸渍，并且在120℃下干燥。
使用等于氧化铝孔体积的100％的溶液体积进行浸渍。
从浆液中取出经浸渍的块体，并在500℃煅烧，以实现铂离子还原成金属。
将如此获得的单元置于氨氧化反应器中。反应条件为：GHSV＝10.000h-1，在催化剂单元入口处所取气体混合物的温度为550℃，压力为1巴，以及空气中氨的浓度等于1％v/v。
氨到NO的转化率高于96％。
对比例1
在与实施例1相同条件下进行的氨氧化反应试验中，使用类似于实施例1中所用的催化剂单元，但该催化剂单元不包含泡沫氧化铝层。
氨到NO的转化率为87％。
对比例2
根据实施例1中已描述的工序制备催化剂单元，该催化剂单元由单个类蜂窝结构陶瓷块体形成，该陶瓷块体具有15cm高度、62胞孔/cm2，并且将该催化剂单元用于与实施例1相同条件下进行的氨氧化反应试验中。
氨到NO的转化率为74％。
Claims (13)
1.用于氨氧化的催化剂，其由一个或多个单元形成，每个单元由具有蜂窝型结构并包含氨氧化催化剂的成对块体形成，每个所述块体具有小于15cm的高度和内置于它们之间并具有开口、随机连接的胞孔的气体渗透性泡沫材料层，该材料层的高度不大于3cm且至少为0.5cm，在该材料层中获得反应物气流的径向混合。
2.根据权利要求1的催化剂单元，其中气体渗透性泡沫材料层为高度小于3cm的泡沫层。
3.根据权利要求1或2的催化剂单元，其中每个块体的高度为2-6cm。
4.根据权利要求1或2的催化剂单元，其中内置层的高度为0.5-2cm。
5.根据权利要求1或2的催化剂单元，其中块体由陶瓷或金属材料形成。
6.根据权利要求5的催化剂单元，其中具有蜂窝型结构的块体的陶瓷材料具有ABO3型钙钛矿结构，其中A为稀土元素或碱土元素或其混合物，B为过渡金属元素或其混合物。
7.根据权利要求1或2的催化剂单元，其中块体具有相同或不同的每cm胞孔数，该胞孔数为3-10，并且其中每cm泡沫层的孔数为4-20。
8.根据权利要求1或2的催化剂单元，其中泡沫层由泡沫氧化铝形成。
9.根据权利要求1或2的催化剂单元，其中氨氧化催化剂为涂层形式，该涂层通过将块体浸渍在包含γ氧化铝的浆液中、从浆液中取出该块体并将其煅烧获得，所述γ氧化铝具有负载于其上的混合氧化物催化剂，该混合氧化物催化剂的组成以CoO、MnO和最低价态的稀土金属氧化物的重量百分数表示为20-45％CoO、50-60％MnO、0.5-20％稀土金属氧化物。
10.根据权利要求7的催化剂单元，其中稀土金属氧化物为La2O3和其与CeO2的混合物。
11.根据权利要求7的催化剂单元，其中块体上存在的催化剂涂层包含0.001-1wt％的Pt。
12.一种氨氧化方法，其中使用的催化剂由一个或多个催化剂单元形成，所述催化剂单元为根据权利要求1-8任一项的催化剂单元。
13.根据权利要求12的一种氨氧化方法，该方法在温度为200℃-900℃、压力为1-12绝对巴、以及GHSV为8.000-140.000h-1下进行。
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| RU2624218C1 (ru) * | 2016-06-08 | 2017-07-03 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Катализатор окисления аммиака |
| DE102017201180A1 (de) * | 2017-01-25 | 2018-07-26 | Thyssenkrupp Ag | Verfahren zur Herstellung von Salpetersäure und dafür geeignete Anlage |
| CN109453769A (zh) * | 2018-10-30 | 2019-03-12 | 中海油太原贵金属有限公司 | 一种钙钛矿氧化物负载铂的氨氧化制氮氧化物的催化剂 |
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| JP5688898B2 (ja) | 2015-03-25 |
| US20100158784A1 (en) | 2010-06-24 |
| EP2202201A1 (en) | 2010-06-30 |
| CN101757953A (zh) | 2010-06-30 |
| US10125020B2 (en) | 2018-11-13 |
| KR20100074004A (ko) | 2010-07-01 |
| PL2202201T3 (pl) | 2016-11-30 |
| BRPI0905173B1 (pt) | 2017-12-26 |
| HRP20160870T1 (hr) | 2016-09-23 |
| KR101671822B1 (ko) | 2016-11-02 |
| JP2010149116A (ja) | 2010-07-08 |
| CA2688949A1 (en) | 2010-06-23 |
| US20130164494A1 (en) | 2013-06-27 |
| SI2202201T1 (sl) | 2016-08-31 |
| ES2582952T3 (es) | 2016-09-16 |
| PT2202201T (pt) | 2016-07-20 |
| EP2202201B1 (en) | 2016-04-20 |
| SG162664A1 (en) | 2010-07-29 |
| CY1117711T1 (el) | 2017-05-17 |
| DK2202201T3 (en) | 2016-08-01 |
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