JP2010069451A - Perovskite type oxidation catalyst and method for producing the same - Google Patents
Perovskite type oxidation catalyst and method for producing the same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 26
- 239000012798 spherical particle Substances 0.000 claims abstract description 21
- 238000001228 spectrum Methods 0.000 claims abstract description 12
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017771 LaFeO Inorganic materials 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- -1 oxide Chemical compound 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910018916 CoOOH Inorganic materials 0.000 description 1
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- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018337 Mn(C2 H3 O2)2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000791 photochemical oxidant Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 208000008842 sick building syndrome Diseases 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Description
本発明はペロブスカイト型酸化物の球状粒子からなる酸化触媒およびその製造方法に関する。 The present invention relates to an oxidation catalyst comprising spherical particles of perovskite oxide and a method for producing the same.
揮発性有機化合物（以下、「ＶＯＣ」と称する。）はシックハウス症候群の原因物質として、また、大気を汚染する浮遊粒子状物質（ＳＰＭ）や光化学オキシダント（ＯX）の原因物質であると考えられており、塗装工場などで、ＶＯＣ排出規制が始まっている。
ＶＯＣの除去についてはＰｔ／アルミナ系触媒を用いて接触燃焼除去する方法が一般的にとられている。また、自動車排ガス触媒についてもアルミナ系の担体に各種貴金属を担持した触媒が実用化されている。しかし、アルミナ担体は高活性であるが、６００℃以上の温度雰囲気にさらされると相転移を起こし始め、失活してしまう。
Volatile organic compounds (hereinafter referred to as “VOC”) are considered to be the causative substances of sick house syndrome, and the causative substances of suspended particulate matter (SPM) and photochemical oxidants (O x ) that pollute the atmosphere. VOC emission regulations have begun in paint factories.
For removal of VOC, a method of catalytic combustion removal using a Pt / alumina catalyst is generally used. Further, as an automobile exhaust gas catalyst, a catalyst in which various noble metals are supported on an alumina carrier has been put into practical use. However, although the alumina carrier is highly active, when it is exposed to an atmosphere having a temperature of 600 ° C. or higher, it begins to undergo phase transition and deactivates.
一方、ペロブスカイト化合物を担体として用いた触媒は耐熱性に優れているが、表面積が小さく、所望の活性を得られにくいと云う問題があった。また、ペロブスカイト型酸化物は焼成に１０００〜１２００℃もの高温を必要とし、製造コストの高い製造方法となっていた。 On the other hand, a catalyst using a perovskite compound as a carrier is excellent in heat resistance, but has a problem that it has a small surface area and it is difficult to obtain a desired activity. In addition, perovskite type oxides require a high temperature of 1000 to 1200 ° C. for firing, and have been a production method with high production costs.
特開昭６３−２２２０１４号公報には、Ｐｂ、Ｚｒ、Ｔｉの各金属イオンを含む硝酸溶液と、尿素を溶解させた水溶液とを混合し、加熱して共沈物を生成させたのち、該共沈物を乾燥し、５００〜１０００℃にて仮焼してつくることを特徴とするペロブスカイト型酸化物微粉末の製造方法が開示されている。しかしながら、このペロブスカイト型酸化物微粉末を触媒としたものは、必ずしも十分な触媒性能を有するものではなかった。
本発明は、従来のペロブスカイト型酸化触媒に比べて、優れた触媒性能を有するペロブスカイト型酸化触媒を提供することを課題とする。 An object of the present invention is to provide a perovskite type oxidation catalyst having superior catalytic performance as compared with conventional perovskite type oxidation catalysts.
本発明のペロブスカイト型酸化触媒は、ペロブスカイト型構造を有する酸化物焼成体からなる球状粒子であって、該粒子の平均粒子径が１０〜５０μｍの範囲、比表面積が１０ｍ2／ｇ〜４０ｍ2／ｇの範囲にあることを特徴とするものである。
前記ペロブスカイト型酸化触媒は、前記ペロブスカイト型構造を有する酸化物焼成体からなる球状粒子のＸ線光電子分光分析法（ＸＰＳ）測定によるＯ１ｓ殻結合エネルギースペクトル図において、ダブレット分裂して低エネルギー側領域に現われるピークの強度（Ａ）と、高エネルギー側の領域に現われるピークの強度（Ｂ）の強度比（Ａ／Ｂ）が１．０〜２．０の範囲にあることが好ましい。
The perovskite type oxidation catalyst of the present invention is a spherical particle made of an oxide fired body having a perovskite type structure, the average particle diameter of the particle is in the range of 10 to 50 μm, and the specific surface area is 10 m 2 / g to 40 m 2 / It is characterized by being in the range of g.
In the O1s shell binding energy spectrum obtained by X-ray photoelectron spectroscopy (XPS) measurement of a spherical particle made of an oxide fired body having the perovskite structure, the perovskite type oxidation catalyst is doublet split into a low energy side region. It is preferable that the intensity ratio (A / B) of the intensity (A) of the peak that appears and the intensity (B) of the peak that appears in the region on the high energy side is in the range of 1.0 to 2.0.
前記ペロブスカイト型構造を有する酸化物焼成体は、ＣａＭｎＯ3、ＬａＣｏＯ3またはＬａＦｅＯ3から選ばれる１種以上であることが好ましい。
前記ペロブスカイト型構造を有する酸化物焼成体からなる球状粒子は、噴霧乾燥により造粒された粒子の焼成体であることが好ましい。
The oxide sintered body having a perovskite structure is preferably at least one selected from CaMnO 3, LaCoO 3 or LaFeO 3.
The spherical particles made of an oxide fired body having a perovskite structure are preferably fired bodies of particles granulated by spray drying.
前記ペロブスカイト型構造を有する酸化物焼成体がＣａＭｎＯ3であり、Ｘ線光電子分光分析法（ＸＰＳ）測定によるＯ１ｓ殻結合エネルギースペクトル図において、５２７．０〜５２９．０ｅＶの領域に現われるピークの強度（Ａ）と５３０．０〜５３２．０ｅＶの領域に現われるピークの強度（Ｂ）の強度比（Ａ／Ｂ）が１．０〜２．０の範囲にあることが好ましい。 The calcined oxide having the perovskite structure is CaMnO 3 , and the peak intensity appearing in the region of 527.0-529.0 eV in the O1s shell binding energy spectrum measured by X-ray photoelectron spectroscopy (XPS) ( It is preferable that the intensity ratio (A / B) of the intensity (B) of the peak appearing in the region of A) and 530.0 to 532.0 eV is in the range of 1.0 to 2.0.
本発明のペロブスカイト型酸化触媒の製造方法は、金属元素が異なる２種類の化学種を１０〜３０℃にて水系溶媒中に混合して固形物含有スラリーを調製し、該固形物を湿式粉砕した後、このスラリーを噴霧乾燥し、７００〜１０００℃にて焼成することを特徴とするものである。
前記湿式粉砕により平均粒子径０．６μｍ以下の固形物とし、前記噴霧乾燥により、平均粒子径１０〜４０μｍの球状粒子を調製することが好ましい。
前記化学種は、塩基性炭酸塩、炭酸塩、酸化物、硝酸塩、シュウ酸塩、酢酸塩、水酸化物、金属アルコキシド、単体金属から選ばれるものであることが好ましい。
In the method for producing a perovskite oxidation catalyst of the present invention, two kinds of chemical species having different metal elements are mixed in an aqueous solvent at 10 to 30 ° C. to prepare a solid-containing slurry, and the solid is wet-pulverized. Thereafter, the slurry is spray-dried and fired at 700 to 1000 ° C.
It is preferable to prepare solid particles having an average particle size of 0.6 μm or less by the wet pulverization and to prepare spherical particles having an average particle size of 10 to 40 μm by the spray drying.
The chemical species is preferably selected from basic carbonates, carbonates, oxides, nitrates, oxalates, acetates, hydroxides, metal alkoxides, and simple metals.
本発明の排気ガス除去用触媒は、前記した何れかの球状粒子に、Ｐｔ、Ｐｄ、Ｒｈ、Ｃｕ、Ｃｒ、ＴｅまたはＢから選ばれる少なくとも１種の金属成分が担持されたことを特徴とするものである。 The exhaust gas removing catalyst of the present invention is characterized in that at least one metal component selected from Pt, Pd, Rh, Cu, Cr, Te or B is supported on any of the spherical particles described above. Is.
本発明に係るペロブスカイト型酸化触媒は、従来の沈殿法などで調製されたペロブスカイト型酸化触媒に比べて、格段に優れた触媒性能を示すことができる。
The perovskite-type oxidation catalyst according to the present invention can exhibit much superior catalyst performance as compared with a perovskite-type oxidation catalyst prepared by a conventional precipitation method or the like.
［ペロブスカイト型酸化触媒］
本発明に係るペロブスカイト型酸化触媒は、ペロブスカイト型構造を有する酸化物焼成体からなる球状粒子であって、該粒子の平均粒子径が１０〜５０μｍの範囲、比表面積が１０ｍ2／ｇ〜４０ｍ2／ｇの範囲にあることを特徴とするものである。
平均粒子径および比表面積がこの範囲にあるペロブスカイト型酸化触媒は、酸化触媒として好適に使用することができる。
前記ペロブスカイト型構造を有する酸化物焼成体は、単一結晶相であることが好ましい。
[Perovskite type oxidation catalyst]
The perovskite type oxidation catalyst according to the present invention is a spherical particle comprising an oxide fired body having a perovskite type structure, the average particle diameter of the particle is in the range of 10 to 50 μm, and the specific surface area is 10 m 2 / g to 40 m 2. / G.
A perovskite type oxidation catalyst having an average particle diameter and a specific surface area in this range can be suitably used as an oxidation catalyst.
The fired oxide body having the perovskite structure is preferably a single crystal phase.
本発明に係るペロブスカイト型酸化触媒は、Ｘ線光電子分光分析法（ＸＰＳ）測定によるＯ１ｓ殻結合エネルギースペクトル図において、ダブレット分裂して低エネルギー側領域に現われるピークの強度（Ａ）と、高エネルギー側の領域に現われるピークの強度（Ｂ）の強度比（Ａ／Ｂ）が１．０〜２．０の範囲にあることが好ましい。 The perovskite type oxidation catalyst according to the present invention has a peak intensity (A) appearing in a low energy side region due to doublet splitting in an O1s shell binding energy spectrum measured by X-ray photoelectron spectroscopy (XPS), and a high energy side. The intensity ratio (A / B) of the intensity (B) of the peak appearing in the region is preferably in the range of 1.0 to 2.0.
一般的なペロブスカイト化合物は、Ｘ線光電子分光分析法（ＸＰＳ）測定した場合、Ｏ１ｓシグナルが、ダブレット分裂することが報告されており、高エネルギー側のＯ１ｓシグナル（Ｏ１ｓ（Ｂ））と低エネルギー側のＯ１ｓシグナル（Ｏ１ｓ（Ａ））に分裂する。この現象は表面酸素（吸着酸素や表面水酸基等）と結晶構造内の酸素の存在に由来するものと考えられることが多い。
ピーク強度比が１未満の場合は、酸化活性が低下する傾向が強くなる。他方、ピーク強度比が２以上である場合を排除するものではないが、通常は１．０〜２．０の範囲にあれば優れた酸化活性を示すことができる。
In general perovskite compounds, it has been reported that the O1s signal undergoes doublet splitting when measured by X-ray photoelectron spectroscopy (XPS), and the O1s signal (O1s (B)) on the high energy side and the low energy side are reported. The O1s signal (O1s (A)) is split. This phenomenon is often considered to be derived from the presence of surface oxygen (such as adsorbed oxygen and surface hydroxyl groups) and oxygen in the crystal structure.
When the peak intensity ratio is less than 1, there is a strong tendency for the oxidation activity to decrease. On the other hand, the case where the peak intensity ratio is 2 or more is not excluded, but usually excellent oxidation activity can be exhibited in the range of 1.0 to 2.0.
前記ペロブスカイト型構造を有する酸化物焼成体の種類については、格別に限定されるものではなく、例えば、後記した原料から生成するペロブスカイト型酸化物を挙げることができる。特に好適には、ＣａＭｎＯ3、ＬａＣｏＯ3またはＬａＦｅＯ3から選ばれるペロブスカイト型酸化物を挙げることができる。 The type of the oxide fired body having the perovskite structure is not particularly limited, and examples thereof include perovskite oxides generated from the raw materials described later. Particularly preferred is a perovskite oxide selected from CaMnO 3 , LaCoO 3 or LaFeO 3 .
ペロブスカイト型構造を有する酸化物焼成体がＣａＭｎＯ3の場合については、前記Ｘ線光電子分光分析法（ＸＰＳ）測定によるＯ１ｓ殻結合エネルギースペクトル図において、５２７．０〜５２９．０ｅＶの領域に現われるピークの強度（Ａ）と５３０．０〜５３２．０ｅＶの領域に現われるピークの強度（Ｂ）の強度比（Ａ／Ｂ）が１．０〜２．０の範囲にあることが好ましい。
前記ペロブスカイト型構造を有する酸化物焼成体からなる球状粒子は、後記した製造方法に示す通り、噴霧乾燥により造粒された粒子の焼成体である。
When the calcined oxide having a perovskite structure is CaMnO 3 , the peak appearing in the region of 527.0-529.0 eV in the O1s shell binding energy spectrum measured by the X-ray photoelectron spectroscopy (XPS) measurement The intensity ratio (A / B) of the intensity (A) and the intensity (B) of the peak appearing in the region of 530.0 to 532.0 eV is preferably in the range of 1.0 to 2.0.
The spherical particles made of an oxide fired body having a perovskite structure are fired bodies of particles granulated by spray drying, as shown in the production method described later.
［ペロブスカイト型酸化触媒の製造方法］
本発明に係るペロブスカイト型酸化物の製造方法は、例えば、炭酸カルシウムと炭酸マンガンなどの様にペロブスカイト型酸化物を形成可能な２種類の化学種を水系で混合してスラリーを調製し、これを湿式粉砕処理した後、該スラリーを噴霧乾燥処理することにより球状粒子を調製し、該球状粒子を焼成するものである。
この様な製造方法により、従来の沈殿法（共沈法）により調製されたペロブスカイト型酸化物に比べて比表面積が高いペロブスカイト型酸化物を得ることができる。また、本発明に係る製造方法により調製されたペロブスカイト型酸化物は、沈殿法により調製されたペロブスカイト型酸化物に比べて、均一性の高いものとなった。
[Production method of perovskite-type oxidation catalyst]
The method for producing a perovskite oxide according to the present invention comprises, for example, preparing a slurry by mixing two kinds of chemical species capable of forming a perovskite oxide such as calcium carbonate and manganese carbonate in an aqueous system. After the wet pulverization treatment, the slurry is spray-dried to prepare spherical particles, and the spherical particles are fired.
By such a production method, it is possible to obtain a perovskite oxide having a specific surface area higher than that of a perovskite oxide prepared by a conventional precipitation method (coprecipitation method). In addition, the perovskite oxide prepared by the manufacturing method according to the present invention has higher uniformity than the perovskite oxide prepared by the precipitation method.
本発明のペロブスカイト型酸化触媒を調製するための原料としては、ＡＢＯ3構造のペロブスカイト型化合物を構成可能なＡに相当する原子とＢに相当する原子をそれぞれ有する化合物であれば、格別限定されるものではない。原子Ａ、Ｂとして、Ｌａ、Ｃｏ、Ｆｅ、Ｃａ、Ｍｎを挙げることができる。また、これらの化合物として、炭酸塩、塩基性炭酸塩、酸化物、硝酸塩、シュウ酸塩、酢酸塩、水酸化物、オキシ水酸化物、金属アルコキシド、単体金属などが使用される。以下に、本発明のペロブスカイト型酸化触媒を調製するための原料として使用可能な化合物について例示するが、これらに限定されるものではない。 The raw material for preparing the perovskite type oxidation catalyst of the present invention is particularly limited as long as it is a compound having an atom corresponding to A and an atom corresponding to B that can constitute a perovskite type compound having an ABO 3 structure. It is not a thing. Examples of the atoms A and B include La, Co, Fe, Ca, and Mn. Further, as these compounds, carbonates, basic carbonates, oxides, nitrates, oxalates, acetates, hydroxides, oxyhydroxides, metal alkoxides, simple metals, and the like are used. Although the compound which can be used as a raw material for preparing the perovskite type | mold oxidation catalyst of this invention below is illustrated, it is not limited to these.
酸化物としては、Ｌａ2Ｏ3、ＣｏＯ、Ｃｏ3Ｏ4、ＦｅＯ、Ｆｅ2Ｏ3、α−Ｆｅ2Ｏ3、Ｆｅ3Ｏ4、Ｆｅ（ＯＨ）（ＣＨ3ＣＯＯ）2、ＣａＯ、ＭｎＯ、ＭｎＯ2、Ｍｎ2Ｏ3、Ｍｎ3Ｏ4、を挙げることができる。
炭酸塩は特に好適であり、Ｌａ2（ＣＯ3）3・８Ｈ2Ｏ、ＣａＣＯ3、ＭｎＣＯ3・ｎＨ2Ｏ 等を挙げることができる。
Examples of the oxide include La 2 O 3 , CoO, Co 3 O 4 , FeO, Fe 2 O 3 , α-Fe 2 O 3 , Fe 3 O 4 , Fe (OH) (CH 3 COO) 2 , CaO, and MnO. , MnO 2 , Mn 2 O 3 , and Mn 3 O 4 .
Carbonates are particularly suitable, La 2 (CO 3 ) 3 · 8H 2 O, CaCO 3 , MnCO 3 · nH 2 O Etc.
硝酸塩としては、Ｌａ2（ＮＯ3）3・６Ｈ2Ｏ、Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ、Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ、Ｃａ（ＮＯ3）2・４Ｈ2Ｏ、Ｍｎ（ＮＯ3）2・６Ｈ2Ｏ、を挙げることができる。
蓚酸塩としては、Ｌａ2（Ｃ2Ｏ4）3・９Ｈ2Ｏ、ＣｏＣ2Ｏ4、ＣａＣ2Ｏ4、ＭｎＣ2Ｏ4、を挙げることができる。
The nitrates include La 2 (NO 3 ) 3 .6H 2 O, Co (NO 3 ) 2 .6H 2 O, Fe (NO 3 ) 3 .9H 2 O, Ca (NO 3 ) 2 .4H 2 O, Mn (NO 3 ) 2 · 6H 2 O.
The oxalate, La 2 (C 2 O 4 ) 3 · 9H 2 O, CoC 2 O 4, CaC 2 O 4, MnC 2 O 4, can be cited.
水酸化物としては、Ｌａ（ＯＨ）3、Ｃｏ（ＯＨ）2、Ｆｅ（ＯＨ）3、Ｃａ（ＯＨ）2、を挙げることができる。
オキシ水酸化物としては、ＣｏＯＯＨ、ＦｅＯＯＨ、を挙げることができる。
塩基性炭酸塩としては、２ＣｏＣＯ3・３Ｃｏ（ＯＨ）2・ｘＨ2Ｏ、を挙げることができる。
酢酸塩としては、Ｃｏ（Ｃ2Ｈ3Ｏ2）2・４Ｈ2Ｏ、Ｃａ（Ｃ2Ｈ3Ｏ2）2・Ｈ2Ｏ、Ｍｎ（Ｃ2Ｈ3Ｏ2）2・４Ｈ2Ｏ、を挙げることができる。
また、ＣａＣ2も使用することができる。
Examples of the hydroxide include La (OH) 3 , Co (OH) 2 , Fe (OH) 3 , and Ca (OH) 2 .
Examples of the oxyhydroxide include CoOOH and FeOOH.
Examples of the basic carbonate include 2CoCO 3 · 3Co (OH) 2 · xH 2 O.
Examples of acetates include Co (C 2 H 3 O 2 ) 2 .4H 2 O, Ca (C 2 H 3 O 2 ) 2 .H 2 O, Mn (C 2 H 3 O 2 ) 2 .4H 2 O, Can be mentioned.
CaC 2 can also be used.
前記スラリーの固形分濃度については、特に制限されるものではないが、例えば、固形分濃度１０〜３０質量％となるように調製される。混合温度については、通常は１０〜３０℃の範囲で混合される。
この様なスラリーについて湿式粉砕処理を行う。
湿式粉砕とは、強力剪断力を加えることができる粉砕機または分散機を用い、スラリー成分のアグロメレーション（塊状化）を防ぎながら分散または粉砕させる操作を意味する。スラリーに含まれる溶媒成分としては、例えば、水、アルコール、ヘキサン、トルエン、塩化メチレン、シリコーン等を挙げることができる。
The solid content concentration of the slurry is not particularly limited, but for example, it is prepared so as to have a solid content concentration of 10 to 30% by mass. About mixing temperature, it mixes normally in the range of 10-30 degreeC.
Such a slurry is subjected to wet pulverization.
The wet pulverization means an operation of dispersing or pulverizing using a pulverizer or a disperser capable of applying a strong shearing force while preventing agglomeration (agglomeration) of slurry components. Examples of the solvent component contained in the slurry include water, alcohol, hexane, toluene, methylene chloride, and silicone.
湿式粉砕に使用する装置としては、本発明の目的を達成できるものであれば格別に限定されるものではないが、例えば、バスケットミル等のバッチ式ビーズミル、横型・縦型・アニュラー型の連続式のビーズミル、サンドグラインダーミル、ボールミル等の湿式媒体攪拌ミル（湿式粉砕機）が例示される。湿式媒体攪拌ミルに用いるビーズとしては、ガラス、アルミナ、ジルコニア、スチール、フリント石等を原料としたビーズが使用可能である。
本発明においては、湿式粉砕処理によりスラリー中の粒子の平均粒子径が０．６μｍ以下にまで処理することが好ましい。０．６μｍ以上の場合、後の工程に適用しても本発明に係るペロブスカイト型酸化触媒を得ることが容易ではない。
The apparatus used for wet pulverization is not particularly limited as long as the object of the present invention can be achieved. For example, a batch type bead mill such as a basket mill, a horizontal type, a vertical type, or an annular type continuous type. Examples thereof include a wet medium stirring mill (wet pulverizer) such as a bead mill, a sand grinder mill, and a ball mill. As beads used in the wet medium agitation mill, beads made of glass, alumina, zirconia, steel, flint stone, or the like can be used.
In the present invention, it is preferable to treat the particles in the slurry to an average particle size of 0.6 μm or less by wet pulverization. In the case of 0.6 μm or more, it is not easy to obtain the perovskite type oxidation catalyst according to the present invention even if it is applied to a later step.
湿式粉砕を終了したスラリーについては、更に噴霧乾燥処理を行うことにより、平均粒子径が１０〜４０μｍの球状粒子を調製する。
前記スラリーの噴霧乾燥処理としては、回転ディスク法、加圧ノズル法、２流体ノズル法など従来公知の方法を採用することができる。特に、特公平２−６１４０６号公報に開示された２流体ノズル方法は、粒子径分布の均一な球状酸化物微粒子集合体を得ることができ、また平均粒子径をコントロールすることが容易であるので好ましい。
About the slurry which complete | finished the wet grinding, the spherical particle | grains with an average particle diameter of 10-40 micrometers are prepared by performing a spray drying process further.
As the slurry spray drying process, a conventionally known method such as a rotating disk method, a pressure nozzle method, or a two-fluid nozzle method can be employed. In particular, the two-fluid nozzle method disclosed in Japanese Examined Patent Publication No. 2-61406 can obtain a spherical oxide fine particle aggregate with a uniform particle size distribution and can easily control the average particle size. preferable.
このときの乾燥温度は、スラリー濃度、処理速度等によっても異なるが、スプレードライヤーを使用する場合、例えば、スプレードライヤーの入口温度としては１００〜３００℃、出口温度４０〜２００℃などの条件が好ましい。
噴霧速度については、格別に制限されるものではないが、通常は噴霧速度０．５〜３Ｌ／分の範囲で行われる。なお、アトマイザー式噴霧乾燥機を使用する場合は、例えば、１００００〜４００００ｒｐｍ（回転数／分）で処理されるが、この範囲に限定されるものではない。
The drying temperature at this time varies depending on the slurry concentration, processing speed, and the like, but when using a spray dryer, for example, the inlet temperature of the spray dryer is preferably 100 to 300 ° C., the outlet temperature of 40 to 200 ° C. .
Although it does not restrict | limit especially about a spray rate, Usually, it carries out in the range of 0.5-3 L / min. In addition, when using an atomizer type spray dryer, although it processes by 10000-40000 rpm (rotation speed / min), for example, it is not limited to this range.
噴霧乾燥処理により得られた球状粒子を温度が７００〜１０００℃で焼成することにより本発明に係るペロブスカイト型酸化触媒を調製することができる。なお、焼成温度については、好適には７００〜９００℃の範囲が推奨される。 The perovskite oxidation catalyst according to the present invention can be prepared by calcining the spherical particles obtained by the spray drying treatment at a temperature of 700 to 1000 ° C. In addition, about the baking temperature, the range of 700-900 degreeC is recommended suitably.
本発明のペロブスカイト型酸化触媒は、自動車排ガス浄化触媒や揮発性有機化合物（ＶＯＣ）除去用酸化触媒として有用である。
The perovskite oxidation catalyst of the present invention is useful as an automobile exhaust gas purification catalyst or an oxidation catalyst for removing volatile organic compounds (VOC).
初めに、本発明で使用した分析方法または測定方法を以下に記す。 First, the analysis method or measurement method used in the present invention will be described below.
［平均粒子径の測定方法］
レーザー回折／散乱方式粒度分布測定装置（堀場製作所製：ＬＡ−７００）にイオン交換水を投入し、試料（ペロブスカイト型酸化触媒）を透過率７５〜９５％となるよう加えた。その後、２ｗｔ％ヘキサメタリン酸ナトリウム水溶液約２０ｍｌを加えて１分間超音波分散を行い、平均粒子径を測定した。
[Measurement method of average particle size]
Ion exchange water was put into a laser diffraction / scattering particle size distribution analyzer (Horiba, Ltd .: LA-700), and a sample (perovskite type oxidation catalyst) was added so as to have a transmittance of 75 to 95%. Thereafter, about 20 ml of a 2 wt% sodium hexametaphosphate aqueous solution was added and subjected to ultrasonic dispersion for 1 minute, and the average particle size was measured.
［比表面積の測定方法］
試料（酸化物焼成粉末）を比表面積測定装置（ユアサアイオニクス製、型番マルチソーブ１２）を用いて窒素吸着法（ＢＥＴ法）を用いて、窒素の吸着量から、ＢＥＴ１点法により比表面積を算出した。
[Measurement method of specific surface area]
The specific surface area of the sample (calcined oxide powder) is calculated from the amount of nitrogen adsorbed using the nitrogen adsorption method (BET method) using a specific surface area measurement device (manufactured by Yuasa Ionics, model number Multisorb 12) by the BET one-point method. did.
［Ｘ線光電子分光分析（ＸＰＳ）測定方法］
試料（酸化物焼成粉末）をサンプルステージ上のカーボンテープに付着させ、日本電子製ＪＰＳ−９０００ＭＣでＸ線源ＡｌＫα線、電圧１０ｋＶ、電流１０ｍＡの条件で測定した。得られたスペクトルはＣ１ｓ（２８４．０ｅＶ）でピーク位置を補正した。
[X-ray photoelectron spectroscopy (XPS) measurement method]
A sample (fired oxide powder) was attached to a carbon tape on a sample stage, and measured with JPS-9000MC manufactured by JEOL under the conditions of an X-ray source AlKα ray, a voltage of 10 kV, and a current of 10 mA. The peak position of the obtained spectrum was corrected with C1s (284.0 eV).
［ＥＰＭＡの測定方法］
試料（ＣａＭｎＯ3の酸化物焼成体からなる粒子）約０．００５ｇについて、島津製作所株式会社製、EPMA-8705を用いて以下の条件にて、粒子表面におけるＭｎ原子及びＣａ原子の濃度を測定した。
測定条件：加速電圧15kv、試料電流0.02μA、測定時間（１ドット辺り）0.007sec、倍率4000倍
ＥＰＭＡによるＭｎ原子またはＣａ原子の濃度測定を５０個の試料（約０．００５ｇ）について行い、特にＭｎ原子の表面濃度のばらつきを調べた。
[Measurement method of EPMA]
About 0.005 g of the sample (particles made of CaMnO 3 oxide fired body), the concentration of Mn atoms and Ca atoms on the particle surface was measured under the following conditions using EPMA-8705 manufactured by Shimadzu Corporation. .
Measurement conditions: accelerating voltage 15 kv, sample current 0.02 μA, measurement time (per dot) 0.007 sec, magnification 4000 times Measurement of concentration of Mn atom or Ca atom by EPMA was performed on 50 samples (about 0.005 g), especially The variation in the surface concentration of Mn atoms was examined.
［実施例１］
１７４．９８ｇのＣａＣＯ3と２１７．７７ｇのＭｎＣＯ3・ｎＨ2Ｏおよび２２２５．５４ｇのイオン交換水を２５℃にて混合し、２６１８．３ｇのスラリーを調製した。
得られたスラリーをビーズ径０．５ｍｍのＺｒビーズ４３０ｃｃを充填した循環方式型湿式粉砕機（アシザワ・ファインテック（株）、LABSTAR）を用い、回転数２４８０ｒｐｍ、循環量１Ｌ／ｍｉｎの条件でスラリー中の固形物の平均粒子径が０．３μｍ以下になるまで粉砕した。
[Example 1]
174.98 g of CaCO 3 , 217.77 g of MnCO 3 .nH 2 O and 2225.54 g of ion exchange water were mixed at 25 ° C. to prepare 2618.3 g of slurry.
Using the circulation type wet pulverizer (Ashizawa Finetech Co., Ltd., LABSTAR) filled with 430cc of Zr beads having a bead diameter of 0.5 mm, the obtained slurry was slurried under the conditions of a rotation speed of 2480 rpm and a circulation rate of 1 L / min. It grind | pulverized until the average particle diameter of the solid substance in it became 0.3 micrometer or less.
その後、循環方式型湿式粉砕機からスラリーを回収し、スラリー中の固形物が沈降しないよう攪拌機で攪拌しながらチューブポンプでスラリーをスプレードライヤー（大川原化工機（株）製、ＬＢ−８型）に供し、入口温度２３０℃、出口温度１１０℃、アトマイザー回転数３００００ｒｐｍの条件で噴霧乾燥を実施し、平均粒子径が１６μｍの球状粒子を得た。なお、得られた球状粒子を以下、「触媒前躯体」と称する。
触媒前躯体をマッフル炉で大気下８００℃、５時間焼成してＣａＭｎＯ3からなるペロブスカイト型酸化触媒を得た。
このペロブスカイト型酸化触媒の走査型電子顕微鏡写真を図３に示す。
Thereafter, the slurry is recovered from the circulation type wet pulverizer, and the slurry is sprayed with a tube pump while stirring with a stirrer so that the solid matter in the slurry does not settle (Okawara Kako Co., Ltd., model LB-8). Then, spray drying was performed under the conditions of an inlet temperature of 230 ° C., an outlet temperature of 110 ° C., and an atomizer rotational speed of 30000 rpm to obtain spherical particles having an average particle diameter of 16 μm. The obtained spherical particles are hereinafter referred to as “catalyst precursor”.
The catalyst precursor was calcined in a muffle furnace at 800 ° C. for 5 hours in the atmosphere to obtain a perovskite type oxidation catalyst made of CaMnO 3 .
A scanning electron micrograph of this perovskite oxidation catalyst is shown in FIG.
続いて、このＣａＭｎＯ3触媒をＸＲＤ、ＢＥＴおよびＸＰＳで分析した。
図１にＣａＭｎＯ3触媒の粉末Ｘ線回折パターンを示す。図１にはＣａＭｎＯ3固有の粉末Ｘ線回折図形が示されており、８００℃、５時間という低温短時間焼成にもかかわらず単一相のペロブスカイト型酸化物の生成が確認された。
ＢＥＴ法により測定された比表面積は１０．８ｍ2／ｇ、平均粒子径は１３μｍであった。
Subsequently, the CaMnO 3 catalyst was analyzed by XRD, BET and XPS.
FIG. 1 shows a powder X-ray diffraction pattern of the CaMnO 3 catalyst. FIG. 1 shows a powder X-ray diffraction pattern specific to CaMnO 3, confirming the formation of a single-phase perovskite oxide in spite of low-temperature short-time firing at 800 ° C. for 5 hours.
The specific surface area measured by the BET method was 10.8 m 2 / g, and the average particle size was 13 μm.
図２にＸ線光電子分光分析法（ＸＰＳ）測定によるＯ１ｓ殻結合エネルギースペクトル図を示す。
図２に示すＸＰＳ測定結果より、得られたＣａＭｎＯ3のＯ１ｓ準位の結合エネルギーのスペクトルは二つに分裂する特徴を持つことが確認された。
低エネルギー側のピーク［Ｏ１ｓ（Ａ）］（ピークトップ：５２８．２ｅＶ、強度：８９０６）と高エネルギー側のピーク［Ｏ１ｓ（Ｂ）］（ピークトップ：５３０．６ｅＶ、強度：６９４２）から、ピーク強度比（Ｏ１ｓ（Ａ）／Ｏ１ｓ（Ｂ））は１．２８と計算された。
また、前記ＥＰＭＡにより、Ｍｎ原子の表面濃度のばらつきを確認したところ、５０個の試料について、Ｍｎ原子表面濃度のばらつきは殆ど見られなかった。
FIG. 2 shows an O1s shell binding energy spectrum obtained by X-ray photoelectron spectroscopy (XPS) measurement.
From the XPS measurement result shown in FIG. 2, it was confirmed that the spectrum of the binding energy of the O1s level of CaMnO 3 obtained has a feature of splitting into two.
From the peak [O1s (A)] (peak top: 528.2 eV, intensity: 8906) on the low energy side and the peak [O1s (B)] (peak top: 530.6 eV, intensity: 6942) on the high energy side The intensity ratio (O1s (A) / O1s (B)) was calculated to be 1.28.
Further, when the variation in the surface concentration of Mn atoms was confirmed by the EPMA, the variation in the surface concentration of Mn atoms was hardly observed for 50 samples.
［触媒性能試験］
ＣａＭｎＯ3触媒ついて流通式触媒反応装置を用いて、プロピレンの酸化反応を行った。反応系に２ｃｃの触媒を充填し、室温から６００℃まで昇温速度５℃／分で昇温しながら、空間速度５００００ｈ-1で４００ｐｐｍのプロピレンを接触させて、出口でガス分析装置を用いてこれらガス成分の濃度測定を行った。
プロピレンの転化率の変化を図４に示した。この結果、後記する比較例１の場合に比べて、優れた転化率を示すことが確認された。
[Catalyst performance test]
With respect to the CaMnO 3 catalyst, propylene oxidation reaction was performed using a flow-type catalytic reactor. The reaction system was charged with 2 cc of catalyst, and 400 ppm of propylene was contacted at a space velocity of 50000 h −1 while raising the temperature from room temperature to 600 ° C. at a heating rate of 5 ° C./min. The concentration of these gas components was measured.
The change in the conversion rate of propylene is shown in FIG. As a result, it was confirmed that an excellent conversion rate was exhibited as compared with Comparative Example 1 described later.
［比較例１］
炭酸ナトリウム２８６．１７ｇを３３７０ｇのイオン交換水に溶解し、６０℃に保持した。また、硝酸カルシウム四水和物１７７．１１ｇと硝酸マンガン２１８．１８ｇを６０℃に保持したイオン交換水２６０６ｇに溶解し、前記炭酸ナトリウム水溶液に４５分で注加した。注加が終了した後、６０℃で１時間沈殿を熟成し、４０℃以下まで冷却した。濾過洗浄を３〜４回繰り返し、濾液伝導度を１００μＳ／ｃｍ以下とした。沈殿物を１２０℃で一晩乾燥し、触媒前躯体を得た。
この触媒前躯体を８００℃、５時間焼成してＣａＭｎＯ3からなるペロブスカイト型酸化触媒を得た。このペロブスカイト型酸化触媒の走査型電子顕微鏡写真を図３に示す。
[Comparative Example 1]
286.17 g of sodium carbonate was dissolved in 3370 g of ion-exchanged water and kept at 60 ° C. In addition, 177.11 g of calcium nitrate tetrahydrate and 218.18 g of manganese nitrate were dissolved in 2606 g of ion-exchanged water maintained at 60 ° C., and poured into the aqueous sodium carbonate solution over 45 minutes. After the addition was completed, the precipitate was aged at 60 ° C. for 1 hour and cooled to 40 ° C. or lower. Filtration washing was repeated 3 to 4 times, and the filtrate conductivity was 100 μS / cm or less. The precipitate was dried at 120 ° C. overnight to obtain a catalyst precursor.
This catalyst precursor was calcined at 800 ° C. for 5 hours to obtain a perovskite oxidation catalyst made of CaMnO 3 . A scanning electron micrograph of this perovskite oxidation catalyst is shown in FIG.
続いて、このＣａＭｎＯ3触媒を実施例１と同様に、ＸＲＤ、ＢＥＴおよびＸＰＳで分析した。
図１に示す粉末Ｘ線回折パターンより、このＣａＭｎＯ3触媒はほぼＣａＭｎＯ3相であるが、僅かに他成分化合物のピークが確認された。比表面積は２．６６ｍ2／ｇであり、その形状は粒子状ではなく、不定形であった。
Subsequently, the CaMnO 3 catalyst was analyzed by XRD, BET and XPS in the same manner as in Example 1.
From the powder X-ray diffraction pattern shown in FIG. 1, this CaMnO 3 catalyst was almost CaMnO 3 phase, but a slight peak of other component compounds was confirmed. The specific surface area was 2.66 m 2 / g, and the shape was not particulate but irregular.
図２に示すＸＰＳ測定結果より、得られたＣａＭｎＯ3のＯ１ｓ準位の結合エネルギーのスペクトルは二つに分裂する特徴を持つことが確認された。
低エネルギー側のピーク［Ｏ１ｓ（Ａ）］（ピークトップ：５２８．２ｅＶ、強度：５９５８）と高エネルギー側のピーク［Ｏ１ｓ（Ｂ）］（ピークトップ：５３０．６ｅＶ、強度：６１６９）から、ピーク強度比（Ｏ１ｓ（Ａ）／Ｏ１ｓ（Ｂ））は０．９７と計算された。
また、前記ＥＰＭＡにより、Ｍｎ原子の表面濃度のばらつきを実施例１と同様に確認したところ、実施例１の場合よりばらつきがあることが確認された。
From the XPS measurement result shown in FIG. 2, it was confirmed that the spectrum of the binding energy of the O1s level of CaMnO 3 obtained has a feature of splitting into two.
From the low energy peak [O1s (A)] (peak top: 528.2 eV, intensity: 5958) and the high energy peak [O1s (B)] (peak top: 530.6 eV, intensity: 6169) The intensity ratio (O1s (A) / O1s (B)) was calculated to be 0.97.
Further, when the variation in the surface concentration of Mn atoms was confirmed in the same manner as in Example 1 by the EPMA, it was confirmed that there was a variation as compared with the case of Example 1.
続いて、このＣａＭｎＯ3触媒について、実施例１と同様に触媒性能試験を行い、その結果を図４に示した。
実施例１と比較例１との対比から、本発明に係るペロブスカイト型酸化物触媒は、沈殿法により調製されたペロブスカイト型酸化物触媒より優れた触媒性能（酸化活性）を示すことが判る。これは、Ｏ１ｓ（Ａ）のピーク強度とＯ１ｓ（Ｂ）のピーク強度の比［Ｏ１ｓ（Ａ）／Ｏ１ｓ（Ｂ）］の大きいペロブスカイト型酸化物触媒が、より強い酸化活性を有することから、優れた触媒性能を発揮するものと推察される。
Subsequently, a catalytic performance test was conducted on the CaMnO 3 catalyst in the same manner as in Example 1, and the results are shown in FIG.
From the comparison between Example 1 and Comparative Example 1, it can be seen that the perovskite oxide catalyst according to the present invention exhibits superior catalyst performance (oxidation activity) than the perovskite oxide catalyst prepared by the precipitation method. This is excellent because the perovskite oxide catalyst having a large ratio [O1s (A) / O1s (B)] of the peak intensity of O1s (A) and the peak intensity of O1s (B) has a stronger oxidation activity. It is presumed that the catalyst performance is exhibited.
Claims (9)
The calcined oxide having the perovskite structure is CaMnO 3 , and the peak intensity appearing in the region of 527.0-529.0 eV in the O1s shell binding energy spectrum measured by X-ray photoelectron spectroscopy (XPS) ( The intensity ratio (A / B) of the intensity (B) of the peak appearing in the region of A) and 530.0 to 532.0 eV is in the range of 1.0 to 2.0. The perovskite type oxidation catalyst according to any one of the above.
7. The chemical species according to claim 6, wherein the chemical species is selected from basic carbonate, carbonate, oxide, nitrate, oxalate, acetate, hydroxide, metal alkoxide, and simple metal. 8. A method for producing a perovskite oxidation catalyst according to 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010195620A (en) * | 2009-02-25 | 2010-09-09 | Nippon Chem Ind Co Ltd | Method for producing calcium-manganese composite oxide |
| JP2019218630A (en) * | 2018-06-19 | 2019-12-26 | 国立研究開発法人産業技術総合研究所 | Method for recovering components to be recovered, perovskite type composite oxide, and device for continuously manufacturing treatment body |
| CN114054020A (en) * | 2021-11-19 | 2022-02-18 | 中国科学院生态环境研究中心 | Perovskite structure material and application thereof in removing formaldehyde at room temperature |
| CN114229987A (en) * | 2021-12-20 | 2022-03-25 | 北京化工大学 | Flat ceramic membrane catalytic oxidation device and process for treating biologically-nondegradable wastewater |
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- 2008-09-22 JP JP2008242070A patent/JP2010069451A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010195620A (en) * | 2009-02-25 | 2010-09-09 | Nippon Chem Ind Co Ltd | Method for producing calcium-manganese composite oxide |
| JP2019218630A (en) * | 2018-06-19 | 2019-12-26 | 国立研究開発法人産業技術総合研究所 | Method for recovering components to be recovered, perovskite type composite oxide, and device for continuously manufacturing treatment body |
| JP7228892B2 (en) | 2018-06-19 | 2023-02-27 | 国立研究開発法人産業技術総合研究所 | Method for recovering components to be recovered, perovskite-type composite oxide, and apparatus for continuously producing treated body |
| CN114054020A (en) * | 2021-11-19 | 2022-02-18 | 中国科学院生态环境研究中心 | Perovskite structure material and application thereof in removing formaldehyde at room temperature |
| CN114229987A (en) * | 2021-12-20 | 2022-03-25 | 北京化工大学 | Flat ceramic membrane catalytic oxidation device and process for treating biologically-nondegradable wastewater |
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