JP5005050B2 - Ammonia gas purification catalyst - Google Patents
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- JP5005050B2 JP5005050B2 JP2010012436A JP2010012436A JP5005050B2 JP 5005050 B2 JP5005050 B2 JP 5005050B2 JP 2010012436 A JP2010012436 A JP 2010012436A JP 2010012436 A JP2010012436 A JP 2010012436A JP 5005050 B2 JP5005050 B2 JP 5005050B2
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- 239000003054 catalyst Substances 0.000 title claims description 79
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 40
- 238000000746 purification Methods 0.000 title description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
Description
本発明は、アンモニアガス浄化用触媒に関する。 The present invention relates to an ammonia gas purification catalyst.
火力発電所などから排出される排ガスには、環境汚染の原因となるアンモニアガスが含まれている。そこで、従来より、アンモニアガスを浄化するための装置の開発が行われており、アンモニア浄化用触媒を用いた装置（例えば、図１６の「アンモニアガス処理装置１６」参照）が知られている。 The exhaust gas discharged from thermal power plants and the like contains ammonia gas that causes environmental pollution. Thus, conventionally, an apparatus for purifying ammonia gas has been developed, and an apparatus using an ammonia purifying catalyst (see, for example, “ammonia gas processing apparatus 16” in FIG. 16) is known.
これらの装置に用いられるアンモニアガス浄化用触媒（例えば、図１７の「触媒層１７」参照）は、一般的に、基材と、基材の表面に担持される多孔質物質と、多孔質物質に保持される触媒成分と、を備えており、その触媒作用によってアンモニアガスを浄化する性能を有する（例えば、特許文献１参照）。 The catalyst for purifying ammonia gas used in these apparatuses (see, for example, “catalyst layer 17” in FIG. 17) generally includes a base material, a porous material supported on the surface of the base material, and a porous material. And has a performance of purifying ammonia gas by its catalytic action (see, for example, Patent Document 1).
ところで、アンモニアガスは、反応式（１）に示す通り、酸素と反応して浄化される。
４ＮＨ３＋３Ｏ２→２Ｎ２＋６Ｈ２Ｏ・・・反応式（１）
しかしながら、従来のアンモニアガス浄化用触媒では、触媒性能の限界から、高いＮＨ３転換率を得ることが困難であり、アンモニアガスを十分に浄化することができなかった。
また、反応式（１）に示される反応においては、副生成物として、Ｎ２Ｏ、ＮＯｘなどが生成してしまう。これらの副生成物は、高温下でその生成量が増加する傾向にあり、しかも、反応式（１）に示される反応は、発熱反応である。そのため、従来のアンモニアガス浄化用触媒では、高いＮ２選択率（すなわち、低いＮ２Ｏ選択率、低いＮＯｘ選択率）を得ることが困難であり、副生成物の生成量を十分に抑制することができなかった。
By the way, the ammonia gas is purified by reacting with oxygen as shown in the reaction formula (1).
4NH 3 + 3O 2 → 2N 2 + 6H 2 O ... Reaction formula (1)
However, with conventional ammonia gas purification catalysts, it is difficult to obtain a high NH 3 conversion rate due to the limit of catalyst performance, and ammonia gas cannot be sufficiently purified.
Further, in the reaction shown in the reaction formula (1), N 2 O, NOx and the like are generated as by-products. The amount of these by-products tends to increase at a high temperature, and the reaction shown in the reaction formula (1) is an exothermic reaction. Therefore, it is difficult to obtain a high N 2 selectivity (that is, a low N 2 O selectivity and a low NOx selectivity) with a conventional ammonia gas purification catalyst, and the amount of by-products generated is sufficiently suppressed. I couldn't.
そこで、本発明は、優れたアンモニアガスの浄化性能を有し、副生成物の生成量を十分に抑制することが可能なアンモニアガス浄化用触媒を提供することを目的とする。 Accordingly, an object of the present invention is to provide an ammonia gas purification catalyst that has excellent ammonia gas purification performance and can sufficiently suppress the amount of by-products produced.
上記課題を解決するために、本発明は、基材と、基材の表面に担持される多孔質物質と、多孔質物質に保持される触媒成分と、を備えたアンモニアガス浄化用触媒であって、前記基材は、三次元的に交差、合流もしくは分岐する多数の微細流路を有するものであり、且つ、前記触媒成分は、Ｐｔ−ＣｕＯ又はＰｄであることを特徴とする。 In order to solve the above problems, the present invention is an ammonia gas purification catalyst comprising a base material, a porous material supported on the surface of the base material, and a catalyst component held by the porous material. The base material has a large number of fine channels that intersect, merge or branch three-dimensionally, and the catalyst component is Pt—CuO or Pd.
また、本発明は、基材と、基材の表面に担持される多孔質物質と、多孔質物質に保持される触媒成分と、を備えたアンモニアガス浄化用触媒であって、前記基材は、三次元的に交差、合流もしくは分岐する多数の微細流路を有するものであり、且つ、前記触媒成分は、Ｐｔ−ＣｕＯ−Ｃｌであることを特徴とする。 Further, the present invention is an ammonia gas purification catalyst comprising a base material, a porous material supported on the surface of the base material, and a catalyst component held by the porous material, wherein the base material is In addition, the catalyst component has a large number of fine channels that intersect, merge, or branch three-dimensionally, and the catalyst component is Pt—CuO—Cl.
また、本発明において、前記微細流路の孔径が３０μｍ〜５００μｍであることを特徴とする。 In the present invention, the fine channel has a pore diameter of 30 μm to 500 μm.
また、本発明において、前記多孔質物質は、酸化アルミニウム（Ａｌ２Ｏ３）であることを特徴とする。 In the present invention, the porous material is aluminum oxide (Al 2 O 3 ).
本発明によれば、優れたアンモニアガスの浄化性能を有し、副生成物の生成量を十分に抑制することが可能なアンモニアガス浄化用触媒を提供することができる。 According to the present invention, it is possible to provide an ammonia gas purification catalyst that has excellent ammonia gas purification performance and can sufficiently suppress the amount of by-products produced.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
＝＝＝アンモニアガス浄化用触媒の基本構成について＝＝＝
まず、本発明の実施形態に係るアンモニアガス浄化用触媒の基本構成について説明する。
=== Basic Configuration of Ammonia Gas Purification Catalyst ===
First, a basic configuration of an ammonia gas purification catalyst according to an embodiment of the present invention will be described.
図１（ａ）は、本発明の実施形態に係るアンモニアガス浄化用触媒を説明するための概略図、図１（ｂ）は、基材（ＳＵＳ）の拡大図である。図１（ａ）に示すアンモニアガス浄化用触媒は、基材（ＳＵＳ）と、基材（ＳＵＳ）の表面に担持される多孔質物質（同図の場合には、酸化アルミニウム（Ａｌ２Ｏ３））と、多孔質物質に保持される触媒成分（Ｐｔ−ＣｕＯ又はＰｄ）と、を備えている。 Fig.1 (a) is the schematic for demonstrating the catalyst for ammonia gas purification which concerns on embodiment of this invention, FIG.1 (b) is an enlarged view of a base material (SUS). The catalyst for purifying ammonia gas shown in FIG. 1A is composed of a base material (SUS) and a porous material supported on the surface of the base material (SUS) (in the case of FIG. 1, aluminum oxide (Al 2 O 3 )) And a catalyst component (Pt—CuO or Pd) retained by the porous material.
図１（ｂ）に示すように、基材（ＳＵＳ）は、いわゆるマイクロ空間を有するマイクロ・パーティション構造を有し、三次元的に交差、合流もしくは分岐する多数の微細流路を有するものである（例えば、特開２００５−２６４１９９号公報、特開２００５−２５４１９４号公報、特開２００５−２５３７９９号公報、特開２００５−３０７９４４号公報など参照）。微細流路の孔径は、３０μｍ〜５００μｍが望ましい。 As shown in FIG. 1 (b), the base material (SUS) has a micro partition structure having a so-called micro space, and has a number of fine flow paths that intersect, merge or branch three-dimensionally. (For example, refer to JP 2005-264199 A, JP 2005-254194 A, JP 2005-253799 A, JP 2005-307944 A, etc.). As for the hole diameter of a microchannel, 30 micrometers-500 micrometers are desirable.
以下の実施例では、アンモニアガス浄化用触媒の一例として、株式会社ナノ・キューブ・ジャパンから提供されたマイクロ・フィン担持触媒を用いた。なお、マイクロ・フィンの直径はすべて１４．８ｍｍである。 In the following examples, a micro fin-supported catalyst provided by Nano Cube Japan Co., Ltd. was used as an example of an ammonia gas purification catalyst. The diameters of the micro fins are all 14.8 mm.
＝＝＝アンモニアガス浄化用触媒の性能について＝＝＝
次に、アンモニアガス浄化用触媒の性能について説明する。
=== About the performance of ammonia gas purification catalyst ===
Next, the performance of the ammonia gas purification catalyst will be described.
本発明者らは、アンモニアガスを浄化する際に、本発明の実施形態に係るアンモニアガス浄化用触媒を用いた場合には、高いＮＨ３転換率を得ることが可能であって、優れたアンモニアガスの浄化性能が得られるとともに、高いＮ２選択率（すなわち、低いＮ２Ｏ選択率、低いＮＯｘ選択率）を得ることも可能であって、副生成物の生成量を十分に抑制することができると考えた。そこで、本発明者らは、このようなアンモニアガス浄化用触媒の性能を確認するために、各種の条件下において触媒性能試験を行った。図２〜図１５に触媒性能試験の結果を示す。これらの触媒性能試験では、高濃度（８，０００ｐｐｍ以上）且つ高ＳＶ（２，０００以上）のアンモニアガスを用いた。 When purifying ammonia gas, the present inventors are able to obtain a high NH 3 conversion rate when using the ammonia gas purifying catalyst according to the embodiment of the present invention. Gas purification performance can be obtained, and high N 2 selectivity (that is, low N 2 O selectivity, low NOx selectivity) can be obtained, and the amount of by-products generated can be sufficiently suppressed. I thought it was possible. Therefore, the present inventors conducted a catalyst performance test under various conditions in order to confirm the performance of such an ammonia gas purification catalyst. 2 to 15 show the results of the catalyst performance test. In these catalyst performance tests, ammonia gas having a high concentration (8,000 ppm or more) and a high SV (2,000 or more) was used.
そして、図２及び図４〜図１１における触媒性能試験では、アンモニアガス浄化用触媒として、図１（ｂ）に示した基材（ＳＵＳ）と、基材（ＳＵＳ）の表面に担持される酸化アルミニウム（Ａｌ２Ｏ３）と、酸化アルミニウム（Ａｌ２Ｏ３）に保持されるＰｔ−ＣｕＯと、を備えたもの（以下「Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒」という。）を用いた。 In the catalyst performance tests in FIGS . 2 and 4 to 11, as the ammonia gas purification catalyst, the base material (SUS) shown in FIG. 1B and the oxidation supported on the surface of the base material (SUS). aluminum (Al 2 O 3), an aluminum oxide (Al 2 O 3) that includes a Pt-CuO held, a (hereinafter referred to as "Pt-CuO-Al 2 O 3 catalyst".).
また、図３及び図１２〜図１５における触媒性能試験では、アンモニアガス浄化用触媒として、図１（ｂ）に示した基材（ＳＵＳ）と、基材（ＳＵＳ）の表面に担持される酸化アルミニウム（Ａｌ２Ｏ３）と、酸化アルミニウム（Ａｌ２Ｏ３）に保持されるＰｄと、を備えたもの（以下「Ｐｄ−Ａｌ２Ｏ３触媒」という。）を用いた。 Further, in the catalyst performance test in FIGS . 3 and 12 to 15, as the ammonia gas purification catalyst, the base material (SUS) shown in FIG. 1B and the oxidation supported on the surface of the base material (SUS). aluminum (Al 2 O 3), was used and Pd retained in aluminum oxide (Al 2 O 3) which, with a (hereinafter referred to as "Pd-Al 2 O 3 catalyst".).
＜Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒を用いた場合＞
（実施例１）
実施例１では、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒及びＰｄ−Ａｌ２Ｏ３触媒について、酸素濃度を変化させた時の触媒活性を調べた。その結果を図２及び図３に示す。なお、実施例１は、ＳＶが７０００ｈ−１、ＮＨ３濃度が７．８％の試験条件で行った。図２及び図３に示すように、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒を用いた場合及びＰｄ−Ａｌ２Ｏ３触媒を用いた場合には、いずれの場合にも、アンモニアガスが高濃度且つ大流量（高ＳＶ）であるにも関わらず、ＮＨ３転換率が高く、しかも、Ｎ２選択率が高くなった。また、酸素濃度が高いほど、ＮＨ３転換率が高くなったが、Ｎ２選択率が低くなった。
<When Pt—CuO—Al 2 O 3 catalyst is used>
Example 1
In Example 1, the catalytic activity of the Pt—CuO—Al 2 O 3 catalyst and Pd—Al 2 O 3 catalyst when the oxygen concentration was changed was examined. The results are shown in FIGS. In addition, Example 1 was performed on test conditions with SV of 7000 h −1 and NH 3 concentration of 7.8%. As shown in FIG. 2 and FIG. 3, in the case of using the Pt—CuO—Al 2 O 3 catalyst and the case of using the Pd—Al 2 O 3 catalyst, in any case, the ammonia gas has a high concentration and Despite the large flow rate (high SV), the NH 3 conversion rate was high and the N 2 selectivity was high. Further, the higher the oxygen concentration, the higher the NH 3 conversion rate, but the lower the N 2 selectivity.
（実施例２）
実施例２では、触媒成分量の影響、すなわちＣｕＯ担持量を変化させて触媒活性に及ぼす影響を調べた。その結果を図４に示す。図４に示すように、ＣｕＯの担持量が増加するほど、Ｐｔ上でのＮＨ３の過剰な酸化が抑制されることとなった。
(Example 2)
In Example 2, the influence of the catalyst component amount, that is, the influence on the catalyst activity by changing the amount of CuO supported was examined. The result is shown in FIG. As shown in FIG. 4, as the amount of CuO supported increases, excessive oxidation of NH 3 on Pt is suppressed.
（実施例３）
実施例３では、触媒成分量の影響、すなわちＰｔ担持量を変化させて触媒活性に及ぼす影響を調べた。その結果を図５に示す。図５に示すように、Ｐｔの担持量が増加するほど、Ｐｔ上でのＮＨ３の過剰な酸化が増加した。また、Ｐｔの担持量が０．１g／ｌの触媒においては、Ｔ１００が高くなり、副生成物であるＮ２Ｏ及びＮＯｘの生成量が多くなった。
(Example 3)
In Example 3, the influence of the catalyst component amount, that is, the influence on the catalyst activity by changing the Pt loading amount was examined. The result is shown in FIG. As shown in FIG. 5, as the amount of Pt supported increased, excessive oxidation of NH 3 on Pt increased. The loading amount of Pt in the catalyst of 0.1 g / l, the higher the T 100, the amount of N 2 O and NOx as a by-product is increased.
（実施例４）
実施例４では、触媒成分源の変化が触媒活性に及ぼす影響を調べた。その結果を図６及び図７に示す。図６及び図７に示すように、塩化白金酸水溶液（Ｈ２ＰｔＣｌ５・４Ｈ２Ｏ）を含浸担持させたＰｔ１−ＣｕＯ１０−Ｃｌは、塩化白金酸水溶液を含浸担持させていないＰｔ１−ＣｕＯ１０よりも、ＮＨ３転換率が高くなるとともに、Ｎ２Ｏ選択率及びＮＯｘ選択率は低くなり、高い活性を示した。
Example 4
In Example 4, the influence of changes in the catalyst component source on the catalyst activity was examined. The results are shown in FIGS. As shown in FIGS. 6 and 7, Pt1-CuO10-Cl to aqueous chloroplatinic acid (H 2 PtCl 5 · 4H 2 O) was loaded by impregnation, from Pt1-CuO10 not impregnated bearing chloroplatinic acid solution In addition, the NH 3 conversion rate increased, and the N 2 O selectivity and NOx selectivity decreased, indicating high activity.
（実施例５）
実施例５では、マイクロ・フィン担持触媒の白金酸化物が触媒活性に及ぼす影響を調べた。その結果を図８及び図９に示す。図８及び図９に示すように、Ｐｔ０．１−ＣｕＯ１０−Ｃｌ−Ｈ触媒では、高いＮＨ３転換率（ほぼ１００％）が得られるとともに、低いＮ２Ｏ選択率（約４％）及び低いＮＯｘ選択率（ほぼ無視し得る程度に低い値）が得られており、極めて高い活性を示した。
(Example 5)
In Example 5, the influence of platinum oxide of the micro-fin supported catalyst on the catalyst activity was examined. The results are shown in FIGS. As shown in FIGS. 8 and 9, the Pt0.1-CuO10-Cl-H catalyst provides high NH 3 conversion (almost 100%), low N 2 O selectivity (about 4%) and low. The NOx selectivity (value almost low enough to be ignored) was obtained, indicating extremely high activity.
（実施例６）
実施例６では、マイクロ・フィン担持触媒の活性と、ハニカム触媒の活性とを比較した。その結果を図１０及び図１１に示す。図１０及び図１１に示すように、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒（Ｐｔ：１ｇ／ｌ、ＣｕＯ：１０ｇ／ｌ、触媒長さ２５ｍｍ）は、ハニカム触媒よりも、Ｎ２Ｏ選択率及びＮＯｘ選択率が低くなり、高い活性を示した。
(Example 6)
In Example 6, the activity of the micro-fin supported catalyst was compared with the activity of the honeycomb catalyst. The results are shown in FIGS. As shown in FIGS. 10 and 11, the Pt—CuO—Al 2 O 3 catalyst (Pt: 1 g / l, CuO: 10 g / l, catalyst length: 25 mm) has a higher N 2 O selectivity than the honeycomb catalyst. The NOx selectivity was low and high activity was exhibited.
＜Ｐｄ−Ａｌ２Ｏ３触媒を用いた場合＞
（実施例７）
実施例７では、Ｐｄ−Ａｌ２Ｏ３触媒について酸素濃度を変化させた時の触媒活性を調べた。その結果を図１２及び図１３に示す。図１２及び図１３に示すように、Ｐｄ−Ａｌ２Ｏ３触媒は、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒よりも、ＮＨ３転換率は高いが、Ｎ２Ｏ選択率及びＮＯｘ選択率はいずれも低くなった。酸素濃度の変化がＰｄ−Ａｌ２Ｏ３触媒に及ぼす影響は、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒の場合とほぼ同様であった。
<When Pd—Al 2 O 3 catalyst is used>
(Example 7)
In Example 7, the catalytic activity of the Pd—Al 2 O 3 catalyst when the oxygen concentration was changed was examined. The results are shown in FIGS. As shown in FIG. 12 and FIG. 13, the Pd—Al 2 O 3 catalyst has a higher NH 3 conversion rate than the Pt—CuO—Al 2 O 3 catalyst, but the N 2 O selectivity and the NOx selectivity are higher. Was also low. The influence of the change in oxygen concentration on the Pd—Al 2 O 3 catalyst was almost the same as that of the Pt—CuO—Al 2 O 3 catalyst.
（実施例８）
実施例８では、Ｐｄ−Ａｌ２Ｏ３触媒について空間速度を変化させた時の触媒活性を調べた。その結果を図１４及び図１５に示す。図１４及び図１５に示すように、Ｐｄ−Ａｌ２Ｏ３触媒は、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒よりも、高い触媒活性を保っており、ＳＶによるＮ２選択率への影響は、ほとんど認められなかった。このことは、Ｐｄ−Ａｌ２Ｏ３触媒が高活性であり、触媒層上端部で反応が完結していることを示唆している。Ｐｄ−Ａｌ２Ｏ３触媒は、Ｐｔ−ＣｕＯ−Ａｌ２Ｏ３触媒よりも、ＮＨ３転換率は高いが、Ｎ２選択率は低かった。
(Example 8)
In Example 8, the catalytic activity of the Pd—Al 2 O 3 catalyst when the space velocity was changed was examined. The results are shown in FIGS. As shown in FIGS. 14 and 15, the Pd—Al 2 O 3 catalyst retains a higher catalytic activity than the Pt—CuO—Al 2 O 3 catalyst, and the effect of SV on N 2 selectivity is Almost not recognized. This suggests that the Pd—Al 2 O 3 catalyst is highly active and the reaction is completed at the upper end of the catalyst layer. Pd-Al 2 O 3 catalyst, than Pt-CuO-Al 2 O 3 catalyst is NH 3 conversion is high, N 2 selectivity of was lower.
Claims (3)
前記基材は、三次元的に交差、合流もしくは分岐する多数の微細流路を有するものであり、且つ、前記触媒成分は、Ｐｔ−ＣｕＯ又はＰｄであって、
前記微細流路の孔径が３０μｍ〜５００μｍであることを特徴とするアンモニアガス浄化用触媒。 A catalyst for purifying ammonia gas comprising a base material, a porous material supported on the surface of the base material, and a catalyst component held by the porous material,
The substrate is three-dimensionally intersect, are those having a number of micro-channel merging or branched, and the catalyst component, I Pt-CuO or Pd der,
A catalyst for purifying ammonia gas, wherein the pore diameter of the fine channel is 30 μm to 500 μm .
前記基材は、マイクロ・フィンであることを特徴とするアンモニアガス浄化用触媒。The catalyst for purifying ammonia gas, wherein the substrate is a micro fin.
前記多孔質物質は、酸化アルミニウム（Ａｌ２Ｏ３）であることを特徴とするアンモニアガス浄化用触媒。 In claim 1 or 2 ,
The catalyst for purifying ammonia gas, wherein the porous material is aluminum oxide (Al 2 O 3 ).
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