JP4248975B2 - Organic compound decomposition catalyst particles and organic compound decomposition method using the same - Google Patents
Organic compound decomposition catalyst particles and organic compound decomposition method using the same Download PDFInfo
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- JP4248975B2 JP4248975B2 JP2003314197A JP2003314197A JP4248975B2 JP 4248975 B2 JP4248975 B2 JP 4248975B2 JP 2003314197 A JP2003314197 A JP 2003314197A JP 2003314197 A JP2003314197 A JP 2003314197A JP 4248975 B2 JP4248975 B2 JP 4248975B2
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- 239000002245 particle Substances 0.000 title claims description 121
- 239000003054 catalyst Substances 0.000 title claims description 89
- 150000002894 organic compounds Chemical class 0.000 title claims description 78
- 238000000354 decomposition reaction Methods 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 85
- 239000010931 gold Substances 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 141
- 235000015165 citric acid Nutrition 0.000 description 47
- 239000007864 aqueous solution Substances 0.000 description 38
- 239000010944 silver (metal) Substances 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- 238000006864 oxidative decomposition reaction Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
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- 238000003786 synthesis reaction Methods 0.000 description 11
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- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910002710 Au-Pd Inorganic materials 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 239000010970 precious metal Substances 0.000 description 4
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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Description
本発明は、有機化合物分解触媒粒子及びそれを用いた有機化合物の分解方法に関し、更に詳しくは、有機化合物の酸化分解反応等に触媒として用いて好適であり、しかも安価な有機化合物分解触媒粒子、及び、この有機化合物分解触媒粒子を用いた有機化合物の分解方法に関するものである。 The present invention relates to an organic compound decomposition catalyst particle and a method for decomposing an organic compound using the same. More specifically, the organic compound decomposition catalyst particle is suitable for use as a catalyst in an oxidative decomposition reaction of an organic compound and the like, and is inexpensive. The present invention also relates to an organic compound decomposition method using the organic compound decomposition catalyst particles.
従来、例えば、排ガス中に含まれる有機化合物を酸化触媒を利用して分解除去することが行われており、この酸化触媒としては、従来より白金（Ｐｔ）触媒が多く用いられている。
一方、貴金属コロイドについても、その触媒性の観点から多くの研究がなされてきており、貴金属コロイドの合成に関しても多くの研究がなされている（非特許文献１、２等参照）。
On the other hand, noble metal colloids have been studied from the viewpoint of their catalytic properties, and many studies have been conducted on the synthesis of noble metal colloids (see Non-Patent Documents 1 and 2).
しかしながら、従来のＰｔ触媒は、有機化合物の酸化分解、特にカルボキシル基を有する有機化合物の分解には、２００℃を超える高温が必要であり、必要なエネルギーの観点、及び、触媒の寿命の観点から、より低温度で有機化合物を酸化分解できる触媒、及び、有機化合物の分解方法が求められていた。
また、従来のＰｔ触媒は、Ｐｔ自体が極めて高価であることから、その用途がＰｔ触媒の価格を問題にしないような分野に限定されてしまうという問題点もある。
一方、貴金属コロイドについても、その触媒性について多くの研究がなされているが、今後重要となってくると思われる５００℃以下の低中温領域での貴金属コロイドの性質についての研究は、ほとんど行われていないのが現状である。
However, the conventional Pt catalyst requires a high temperature exceeding 200 ° C. for oxidative decomposition of an organic compound, particularly decomposition of an organic compound having a carboxyl group, from the viewpoint of required energy and the life of the catalyst. Therefore, a catalyst capable of oxidatively decomposing an organic compound at a lower temperature and a method for decomposing the organic compound have been demanded.
In addition, since the conventional Pt catalyst is extremely expensive, there is a problem that its use is limited to a field where the price of the Pt catalyst is not a problem.
On the other hand, there are many studies on the catalytic properties of precious metal colloids, but almost no research has been conducted on the properties of precious metal colloids in the low and intermediate temperature range below 500 ° C, which is expected to become important in the future. The current situation is not.
本発明は、上記の課題を解決するためになされたものであって、有機化合物、特にカルボキシル基を有する有機化合物を２００℃以下の温度にて酸化分解することができ、しかも、白金に比べて安価な貴金属粒子を用いることができる有機化合物分解触媒粒子及びそれを用いた有機化合物の分解方法を提供することを目的とする。 The present invention has been made to solve the above-described problems, and can oxidatively decompose an organic compound, particularly an organic compound having a carboxyl group, at a temperature of 200 ° C. or lower, and compared with platinum. An object of the present invention is to provide an organic compound decomposition catalyst particle capable of using inexpensive precious metal particles and an organic compound decomposition method using the same.
本発明者は、鋭意検討を行った結果、１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含む粒子が、有機化合物、特にカルボキシル基を含む有機化合物を２００℃以下にて酸化分解し得ることを発見し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that particles containing 5% by weight or more each of two or more elements selected from the group of gold, silver, and palladium in one particle are organic compounds, particularly carboxyl groups. It has been found that an organic compound containing can be oxidized and decomposed at 200 ° C. or lower, and the present invention has been completed.
すなわち、本発明の有機化合物分解触媒粒子は、カルボキシル基を含む有機化合物を２００℃以下の温度下にて分解する触媒粒子であって、１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含有してなることを特徴とする。
前記粒子の粒子径は、５ｎｍ以上かつ２０ｎｍ以下であることが好ましい。
前記粒子は、金属酸化物に担持されていることが好ましい。
前記粒子は、金、銀、パラジウムの群から選択された２種以上の元素を含む金属塩水溶液を還元してなることが好ましい。
That is, the organic compound decomposition catalyst particle of the present invention is a catalyst particle that decomposes an organic compound containing a carboxyl group at a temperature of 200 ° C. or less, and is selected from the group of gold, silver, and palladium in one particle. Each of the two or more elements is contained in an amount of 5% by weight or more.
The particle diameter of the particles is preferably 5 nm or more and 20 nm or less.
The particles are preferably supported on a metal oxide.
The particles are preferably formed by reducing an aqueous metal salt solution containing two or more elements selected from the group consisting of gold, silver and palladium.
本発明の有機化合物の分解方法は、１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含有する有機化合物分解触媒粒子に、１００℃以上かつ２００℃以下の温度にてカルボキシル基を含む有機化合物を接触させ、該有機化合物を分解させることを特徴とする。 The organic compound decomposition method of the present invention is such that the organic compound decomposition catalyst particles each containing 5% by weight or more of two or more elements selected from the group of gold, silver, and palladium in one particle are at least 100 ° C. In addition, the organic compound containing a carboxyl group is brought into contact at a temperature of 200 ° C. or lower to decompose the organic compound.
本発明の有機化合物分解触媒粒子によれば、１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含有するので、２００℃以下の低中温領域においてもカルボキシル基を含む有機化合物を分解することができる。しかも、白金より安価な金属である金、銀、パラジウムを用いたので、触媒の低価格を図ることができ、工業上非常に有益なものとなる。 According to the organic compound decomposition catalyst particles of the present invention, each particle contains 5% by weight or more of two or more elements selected from the group of gold, silver, and palladium. Even in the region, an organic compound containing a carboxyl group can be decomposed. In addition, since gold, silver, and palladium, which are cheaper than platinum, are used, the cost of the catalyst can be reduced, which is very useful industrially.
本発明の有機化合物の分解方法によれば、１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含有する有機化合物分解触媒粒子に、１００℃以上かつ２００℃以下の温度にてカルボキシル基を含む有機化合物を接触させ、該有機化合物を分解させるので、２００℃以下の低中温領域においてもカルボキシル基を含む有機化合物を容易かつ速やかに分解することができる。
According to the organic compound decomposition method of the present invention, the organic compound decomposition catalyst particles each containing 5% by weight or more of two or more elements selected from the group of gold, silver, and palladium in 100 Since an organic compound containing a carboxyl group is brought into contact with and decomposed at a temperature of ℃ to 200 ° C, the organic compound containing a carboxyl group is easily and quickly decomposed even in a low and medium temperature region of 200 ° C or less. be able to.
本発明の有機化合物分解触媒粒子及びそれを用いた有機化合物の分解方法の最良の形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The best mode of the organic compound decomposition catalyst particles of the present invention and the organic compound decomposition method using the same will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
［有機化合物分解触媒粒子］
本発明の有機化合物分解触媒粒子は、１つの粒子中に、金（Ａｕ）、銀（Ａｇ）、パラジウム（Ｐｄ）の群から選択された２種以上の元素を含有するものであり、選択された２種以上の元素の含有量は、それぞれが５重量％以上である。
[Organic compound decomposition catalyst particles]
The organic compound decomposition catalyst particles of the present invention contain two or more elements selected from the group of gold (Au), silver (Ag), and palladium (Pd) in one particle, and are selected. The content of two or more elements is 5% by weight or more.
これらの元素は、１つの粒子中に共存していることが必要であるが、これらの元素は合金化されていても、されていなくても、どちらでもよい。また、選択された２種以上の元素の含有量は、それぞれが２０重量％以上であることがより好ましい。
ここで、１つの粒子中に、Ａｕ、Ａｇ、Ｐｄの群から選択された２種以上の元素を含有するとは、例えば、ＡｕとＡｇを選択した場合、１つの粒子中に、Ａｕを５重量％以上、Ａｇを５重量％以上、それぞれ含有するという意味である。
These elements need to coexist in one particle, but these elements may or may not be alloyed. Further, the content of the two or more selected elements is more preferably 20% by weight or more.
Here, when two or more elements selected from the group of Au, Ag, and Pd are contained in one particle, for example, when Au and Ag are selected, 5 weight of Au is contained in one particle. % Or more and 5% by weight or more of Ag.
この有機化合物分解触媒粒子は、１つの粒子中に、Ａｕ、Ａｇ、Ｐｄの群から選択された２種以上の元素をそれぞれ５重量％以上含有するものであればよく、他の成分は特に限定されないが、Ａｕ、Ａｇ、Ｐｄの群から選択された２種以上の元素のみからなることが好ましい。 The organic compound decomposition catalyst particles only need to contain 5% by weight or more of each of two or more elements selected from the group of Au, Ag, and Pd in one particle, and other components are particularly limited. Although it is not, it is preferable that it consists only of 2 or more types of elements selected from the group of Au, Ag, and Pd.
この有機化合物分解触媒粒子は、所定の粒子径の範囲で最大（もしくは極大）の触媒活性を示すものが好ましく、この観点から、粒子径は、５ｎｍ以上かつ２０ｎｍ以下が好ましく、より好ましくは、５ｎｍ以上かつ１０ｎｍ以下である。
その理由は、粒径が２０ｎｍを超えると表面積が小さくなるため、十分な量の有機物を吸着することができなくなるからであり、また、粒径が５ｎｍ未満では、粒子の表面における活性が高いために、化学的反応性に富んだものとなる一方、表面エネルギーの増大とともに不安定になるために、触媒反応温度での有機化合物分解触媒粒子同士の不必要な融着が生じる虞があるからである。
The organic compound decomposition catalyst particles preferably exhibit the maximum (or maximum) catalytic activity within a predetermined particle diameter range. From this viewpoint, the particle diameter is preferably 5 nm or more and 20 nm or less, more preferably 5 nm. Above and below 10 nm.
The reason is that when the particle size exceeds 20 nm, the surface area becomes small, so that a sufficient amount of organic matter cannot be adsorbed. When the particle size is less than 5 nm, the activity on the particle surface is high. On the other hand, because it becomes rich in chemical reactivity, it becomes unstable as the surface energy increases, so there is a possibility that unnecessary fusion between organic compound decomposition catalyst particles at the catalytic reaction temperature may occur. is there.
この有機化合物分解触媒粒子は、酸化アルミニウム（アルミナ）、酸化ケイ素（シリカ）、安定化した酸化ジルコニウム（安定化ジルコニア）等の金属酸化物に担持させて使用することもできる。この場合、この有機化合物分解触媒粒子を、酸化アルミニウム（アルミナ）等の金属酸化物担体に対して１重量％以上担持させれば、有機化合物を酸化分解する触媒として使用することができる。 The organic compound decomposition catalyst particles can be used by being supported on a metal oxide such as aluminum oxide (alumina), silicon oxide (silica), stabilized zirconium oxide (stabilized zirconia), or the like. In this case, if the organic compound decomposition catalyst particles are supported on a metal oxide carrier such as aluminum oxide (alumina) in an amount of 1% by weight or more, the organic compound decomposition catalyst particles can be used as a catalyst for oxidative decomposition of the organic compound.
［有機化合物分解触媒粒子の製造方法］
この有機化合物分解触媒粒子は、湿式、乾式を問わず製造することができるが、以下のような方法により製造するのが好適である。
まず、上記の有機化合物分解触媒粒子を構成する複数の貴金属元素それぞれの貴金属塩を含む水溶液を作成し、さらに、貴金属コロイドの分散安定剤を添加した後、この水溶液に水素化硼素ナトリウム等の還元剤を加え、含まれる貴金属塩を同時に還元することにより、容易かつ速やかに作製することができる。
[Method for producing organic compound decomposition catalyst particles]
The organic compound decomposition catalyst particles can be produced regardless of wet type or dry type, but is preferably produced by the following method.
First, an aqueous solution containing a noble metal salt of each of a plurality of noble metal elements constituting the organic compound decomposition catalyst particles is prepared, and further, a dispersion stabilizer of a noble metal colloid is added, and then the aqueous solution such as sodium borohydride is reduced. By adding an agent and reducing the contained noble metal salt at the same time, it can be easily and quickly produced.
［有機化合物の分解方法］
この有機化合物の分解方法は、１つの粒子中に、Ａｕ、Ａｇ、Ｐｄの群から選択された２種以上の元素をそれぞれ５重量％以上含有する有機化合物分解触媒粒子に、１００℃以上かつ２００℃以下の温度にて有機化合物を接触させ、該有機化合物を分解させる方法である。
[Decomposition method of organic compounds]
In this organic compound decomposition method, organic compound decomposition catalyst particles each containing 5% by weight or more of two or more elements selected from the group of Au, Ag, and Pd in one particle are heated to 100 ° C. or higher and 200 ° C. This is a method in which an organic compound is brought into contact at a temperature of 0 ° C. or lower to decompose the organic compound.
有機化合物を接触させる条件としては、上記の有機化合物分解触媒粒子に２００℃以下の温度下で有機化合物を接触させれば十分であり、分解の際の雰囲気としては、酸化性雰囲気、不活性雰囲気のいずれも適用することができる。特に、不活性雰囲気の場合、酸素が存在しないにもかかわらず、酸化分解反応を好適に生じさせることができる。また、その際、コンプレッサ等の空気圧縮機等を用いて加圧する必要はなく、常圧下で十分に有機化合物の酸化分解反応を生じさせることができる。 As the conditions for contacting the organic compound, it is sufficient that the organic compound is brought into contact with the organic compound decomposition catalyst particles at a temperature of 200 ° C. or less. The atmosphere during the decomposition includes an oxidizing atmosphere and an inert atmosphere. Any of these can be applied. In particular, in the case of an inert atmosphere, an oxidative decomposition reaction can be suitably caused even though oxygen is not present. Further, at that time, it is not necessary to pressurize using an air compressor such as a compressor, and an oxidative decomposition reaction of an organic compound can be sufficiently caused under normal pressure.
特に、カルボキシル基を有する有機化合物の場合、２００℃以下の温度下で、常圧で、分解の際の雰囲気中に酸素が存在しなくても、好適に酸化分解を行うことができる。
カルボキシル基を有する有機化合物としては、カルボキシル基をその分子内に含有する有機化合物であればよく、低分子であるか、高分子であるかは問わず、酸化性雰囲気、不活性雰囲気のいずれにおいても分解することができる。
例えば、飽和脂肪族モノカルボン酸、飽和脂肪族ジ（あるいはトリ）カルボン酸、不飽和脂肪酸、炭素環カルボン酸、複素環カルボン酸、あるいはこれらの塩等を効率よく分解することができる。
In particular, in the case of an organic compound having a carboxyl group, oxidative decomposition can be suitably carried out at a temperature of 200 ° C. or lower at normal pressure and without oxygen in the atmosphere during decomposition.
The organic compound having a carboxyl group may be an organic compound containing a carboxyl group in the molecule, regardless of whether it is a low molecule or a polymer, in an oxidizing atmosphere or an inert atmosphere. Can also be decomposed.
For example, saturated aliphatic monocarboxylic acid, saturated aliphatic di (or tri) carboxylic acid, unsaturated fatty acid, carbocyclic carboxylic acid, heterocyclic carboxylic acid, or salts thereof can be efficiently decomposed.
飽和脂肪族モノカルボン酸としては、蟻酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、ピバル酸、ラウリン酸、パルミチン酸、ステアリン酸等が挙げられる。
飽和脂肪族ジ（あるいはトリ）カルボン酸としては、シュウ酸、マロン酸、コハク酸、リンゴ酸、クエン酸、酒石酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸等が挙げられる。
Examples of the saturated aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, palmitic acid, stearic acid and the like.
Examples of the saturated aliphatic di (or tri) carboxylic acid include oxalic acid, malonic acid, succinic acid, malic acid, citric acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, and suberic acid.
不飽和脂肪酸としては、アクリル酸、ポリアクリル酸、プロピオン酸、メタクリル酸、クロトン酸、オレイン酸、マレイン酸、フマル酸等が挙げられる。
炭素環カルボン酸としては、安息香酸、フタル酸、イソフタル酸、テレフタル酸等が挙げられる。
複素環カルボン酸としては、ニコチン酸、イソニコチン酸等が挙げられる。
Examples of the unsaturated fatty acid include acrylic acid, polyacrylic acid, propionic acid, methacrylic acid, crotonic acid, oleic acid, maleic acid, and fumaric acid.
Examples of the carbocyclic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
Examples of the heterocyclic carboxylic acid include nicotinic acid and isonicotinic acid.
以下、実施例１〜９及び比較例１〜３により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely by Examples 1-9 and Comparative Examples 1-3, this invention is not limited by these Examples.
［有機化合物分解触媒粒子の合成］
下記の５種類の有機化合物分解触媒粒子を合成した。
（Ａ）Ａｇ−ＰｄコロイドによるＡｇ−Ｐｄ触媒粒子（１）の合成
（Ａｇ：Ｐｄ＝５０：５０）
ＡｇＮＯ３とＰｄ（ＮＯ３）２水溶液を所定量混合して金属成分であるＡｇ及びＰｄの総量が０．０３ｗｔ％の水溶液を作製し、さらに、Ａｇ及びＰｄの総量に対してクエン酸３ナトリウム２水和物を等モル量となるように添加・溶解して原料用水溶液とした。
一方、ＮａＢＨ４の含有量が原料用水溶液のＡｇ及びＰｄの総量に対して０．５モル量となるように、このＮａＢＨ４を純水に溶解し還元用水溶液を作製した。
[Synthesis of organic compound decomposition catalyst particles]
The following five types of organic compound decomposition catalyst particles were synthesized.
(A) Synthesis of Ag-Pd catalyst particles (1) by Ag-Pd colloid (Ag: Pd = 50: 50)
A predetermined amount of AgNO 3 and Pd (NO 3 ) 2 aqueous solution are mixed to prepare an aqueous solution in which the total amount of Ag and Pd as metal components is 0.03 wt%, and trisodium citrate with respect to the total amount of Ag and Pd. Dihydrate was added and dissolved so as to have an equimolar amount to obtain a raw material aqueous solution.
On the other hand, this NaBH 4 was dissolved in pure water so that the content of NaBH 4 was 0.5 molar relative to the total amount of Ag and Pd in the raw material aqueous solution to prepare a reducing aqueous solution.
次いで、上記の原料用水溶液を４０℃に加温した後、この原料用水溶液に還元用水溶液を５分間掛けて滴下させ、反応溶液を作製した。
次いで、この反応溶液の還元反応を促進させた。この還元反応は、上記の反応溶液を３０分間、４０℃に保ったまま撹拝して反応を促進させた。
反応終了後、この反応溶液を限外ろ過モジュール（旭化成社製）を用いて濃縮・脱イオン処理を行い、約３０倍に濃縮した。この濃縮した反応溶液からフリーズドドライ法により固形分を採取した。
以上により、１つの粒子が、ＡｇとＰｄからなり、その割合が５０：５０であるＡｇ−Ｐｄ触媒粒子（１）を得た。
Subsequently, after heating said raw material aqueous solution to 40 degreeC, the aqueous solution for reduction was dripped at this aqueous solution for raw materials over 5 minutes, and the reaction solution was produced.
Subsequently, the reduction reaction of this reaction solution was promoted. In this reduction reaction, the reaction solution was stirred for 30 minutes while maintaining the temperature at 40 ° C. to promote the reaction.
After completion of the reaction, the reaction solution was concentrated and deionized using an ultrafiltration module (Asahi Kasei Co., Ltd.) and concentrated about 30 times. A solid content was collected from the concentrated reaction solution by freeze-drying.
As described above, Ag—Pd catalyst particles (1) in which one particle is composed of Ag and Pd and the ratio is 50:50 were obtained.
（Ｂ）Ａｕ−ＰｄコロイドによるＡｕ−Ｐｄ触媒粒子（１）の合成
（Ａｕ：Ｐｄ＝５０：５０）
Ａｕ源としてＨＡｕＣｌ４水溶液、Ｐｄ源としてＰｄ（ＮＯ３）２水溶液を用いた以外は、上記（Ａ）のＡｇ−Ｐｄ触媒粒子（１）の合成と同様にして、１つの粒子がＡｕとＰｄからなり、その割合が５０：５０であるＡｕ−Ｐｄ触媒粒子（１）を得た。
(B) Synthesis of Au—Pd catalyst particles (1) by Au—Pd colloid (Au: Pd = 50: 50)
Except for using an HAuCl 4 aqueous solution as the Au source and a Pd (NO 3 ) 2 aqueous solution as the Pd source, one particle is made of Au and Pd in the same manner as in the synthesis of the Ag—Pd catalyst particles (1) in (A) above. Au-Pd catalyst particles (1) having a ratio of 50:50 were obtained.
（Ｃ）Ａｕ−ＡｇコロイドによるＡｕ−Ａｇ触媒粒子（１）の合成
（Ａｕ：Ａｇ＝５０：５０）
Ａｕ源としてＮａ３Ａｕ（ＳＯ３）２水溶液、Ａｇ源としてＡｇＮＯ３水溶液を用いた以外は、上記（Ａ）のＡｇ−Ｐｄ触媒粒子（１）の合成と同様にして、１つの粒子がＡｕとＡｇからなり、その割合が５０：５０であるＡｕ−Ａｇ触媒粒子（１）を得た。
(C) Synthesis of Au-Ag catalyst particles (1) by Au-Ag colloid (Au: Ag = 50: 50)
Except for using an aqueous Na 3 Au (SO 3 ) 2 solution as an Au source and an AgNO 3 aqueous solution as an Ag source, one particle is Au in the same manner as in the synthesis of the Ag—Pd catalyst particles (1) in (A) above. Au—Ag catalyst particles (1) having a ratio of 50:50 were obtained.
（Ｄ）Ａｇ−ＰｄコロイドによるＡｇ−Ｐｄ触媒粒子（２）の合成
（Ａｇ：Ｐｄ＝７５：２５）
Ａｇ源としてＡｇＮＯ３水溶液、Ｐｄ源としてＰｄ（ＮＯ３）２水溶液を用い、その比をＡｇ：Ｐｄ＝７５：２５とした以外は、上記（Ａ）のＡｇ−Ｐｄ触媒粒子（１）の合成と同様にして、１つの粒子がＡｇとＰｄからなり、その割合が７５：２５であるＡｇ−Ｐｄ触媒粒子（２）を得た。
(D) Synthesis of Ag-Pd catalyst particles (2) by Ag-Pd colloid (Ag: Pd = 75: 25)
Synthesis of Ag-Pd catalyst particles (1) in (A) above, except that an AgNO 3 aqueous solution is used as the Ag source, a Pd (NO 3 ) 2 aqueous solution is used as the Pd source, and the ratio is set to Ag: Pd = 75: 25 In the same manner as above, Ag—Pd catalyst particles (2) in which one particle is composed of Ag and Pd and the ratio is 75:25 were obtained.
（Ｅ）Ａｇ−ＰｄコロイドによるＡｇ−Ｐｄ触媒粒子（３）の合成
（Ａｇ：Ｐｄ＝２５：７５）
Ａｇ源としてＡｇＮＯ３水溶液、Ｐｄ源としてＰｄ（ＮＯ３）２水溶液を用い、その比をＡｇ：Ｐｄ＝２５：７５とした以外は、上記（Ａ）のＡｇ−Ｐｄ触媒粒子（１）の合成と同様にして、１つの粒子がＡｇとＰｄからなり、その割合が２５：７５であるＡｇ−Ｐｄ触媒粒子（３）を得た。
(E) Synthesis of Ag-Pd catalyst particles (3) by Ag-Pd colloid (Ag: Pd = 25: 75)
Synthesis of Ag-Pd catalyst particles (1) of (A) above, except that an AgNO 3 aqueous solution is used as the Ag source, a Pd (NO 3 ) 2 aqueous solution is used as the Pd source, and the ratio is set to Ag: Pd = 25: 75 In the same manner as described above, Ag—Pd catalyst particles (3) in which one particle is composed of Ag and Pd and the ratio is 25:75 were obtained.
［有機化合物の分解］
上記の５種類の有機化合物分解触媒粒子（Ａｇ−Ｐｄ触媒粒子（１）〜Ａｇ−Ｐｄ触媒粒子（３））を用いて有機化合物の分解を行った。
（実施例１）
クエン酸水溶液に上記（Ａ）で得られたＡｇ−Ｐｄ触媒粒子（１）を添加し、このＡｇ−Ｐｄ触媒粒子（１）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部のクエン酸が吸着していた。
[Decomposition of organic compounds]
The organic compound was decomposed using the above five kinds of organic compound decomposition catalyst particles (Ag—Pd catalyst particles (1) to Ag—Pd catalyst particles (3)).
Example 1
The Ag—Pd catalyst particles (1) obtained in (A) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Ag—Pd catalyst particles (1) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (1).
この試料を、空気中、１４０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を熱分析装置により確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。なお、通常の状態でのクエン酸の分解温度は３５０℃である。 When this sample was allowed to stand in air at 140 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component in the remaining sample was confirmed by a thermal analyzer, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed. In addition, the decomposition temperature of citric acid in a normal state is 350 ° C.
（実施例２）
上記（Ａ）で得られたＡｇ−Ｐｄ触媒粒子（１）を、酸化アルミニウム粒子１００重量部に対し１重量部担持させた。
次いで、クエン酸水溶液に、この酸化アルミニウム粒子に担持されたＡｇ−Ｐｄ触媒粒子（１）を添加し、この酸化アルミニウム粒子に担持されたＡｇ−Ｐｄ触媒粒子（１）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 2)
1 part by weight of the Ag—Pd catalyst particles (1) obtained in the above (A) was supported on 100 parts by weight of the aluminum oxide particles.
Next, Ag-Pd catalyst particles (1) supported on the aluminum oxide particles are added to the citric acid aqueous solution, and citric acid is added to the Ag-Pd catalyst particles (1) supported on the aluminum oxide particles. Adsorbed inside.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (1).
この試料を、空気中、１８０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 180 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例３）
クエン酸水溶液に上記（Ａ）で得られたＡｇ−Ｐｄ触媒粒子（１）を添加し、このＡｇ−Ｐｄ触媒粒子（１）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 3)
The Ag—Pd catalyst particles (1) obtained in (A) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Ag—Pd catalyst particles (1) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (1).
この試料を、空気中、２００℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 200 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例４）
クエン酸水溶液に上記（Ｂ）で得られたＡｕ−Ｐｄ触媒粒子（１）を添加し、このＡｕ−Ｐｄ触媒粒子（１）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｕ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 4)
The Au—Pd catalyst particles (1) obtained in (B) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Au—Pd catalyst particles (1) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Au—Pd catalyst particles (1).
この試料を、空気中、１８０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 180 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例５）
クエン酸水溶液に上記（Ｃ）で得られたＡｕ−Ａｇ触媒粒子（１）を添加し、このＡｕ−Ａｇ触媒粒子（１）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｕ−Ａｇ触媒粒子（１）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 5)
The Au-Ag catalyst particles (1) obtained in (C) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Au-Ag catalyst particles (1) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Au—Ag catalyst particles (1).
この試料を、空気中、２００℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 200 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例６）
クエン酸水溶液に上記（Ｄ）で得られたＡｇ−Ｐｄ触媒粒子（２）を添加し、このＡｇ−Ｐｄ触媒粒子（２）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（２）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 6)
The Ag—Pd catalyst particles (2) obtained in (D) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Ag—Pd catalyst particles (2) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (2).
この試料を、空気中、１５０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 150 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in a substantially stoichiometric amount as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例７）
クエン酸水溶液に上記（Ｅ）で得られたＡｇ−Ｐｄ触媒粒子（３）を添加し、このＡｇ−Ｐｄ触媒粒子（３）に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（３）１００重量部に対し約５重量部のクエン酸が吸着していた。
(Example 7)
The Ag—Pd catalyst particles (3) obtained in (E) above were added to the citric acid aqueous solution, and citric acid was adsorbed on the Ag—Pd catalyst particles (3) in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (3).
この試料を、空気中、１８０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を実施例１と同様にして確認したところ、炭素成分の残存は認められず、クエン酸が完全に酸化分解していることが確認された。 When this sample was allowed to stand in air at 180 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in almost stoichiometric amounts as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed in the same manner as in Example 1, no carbon component remained, and it was confirmed that citric acid was completely oxidatively decomposed.
（実施例８）
吸着する有機化合物をクエン酸からシュウ酸ナトリウム（カルボン酸塩）に変更した以外は、実施例１と同様にして、Ａｇ−Ｐｄ触媒粒子（１）に、シュウ酸ナトリウムを、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部のシュウ酸ナトリウムが吸着していた。
(Example 8)
Adsorbing sodium oxalate on Ag-Pd catalyst particles (1) in an aqueous solution in the same manner as in Example 1 except that the adsorbing organic compound was changed from citric acid to sodium oxalate (carboxylate). I let you.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of sodium oxalate was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (1).
この試料を、空気中、１５０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を熱分析装置により確認したところ、炭素成分の残存は認められず、シュウ酸ナトリウムのうちの有機成分（オキサリル：カルボキシル基）が完全に酸化分解していることが確認された。
なお、通常の状態でのシュウ酸ナトリウムの分解温度は３００℃以上である。
When this sample was allowed to stand in air at 150 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in a substantially stoichiometric amount as a gas. When the remaining amount of the carbon component of the remaining sample was confirmed by a thermal analyzer, no carbon component remained, and the organic component (oxalyl: carboxyl group) of sodium oxalate was completely oxidatively decomposed. Was confirmed.
In addition, the decomposition temperature of sodium oxalate in a normal state is 300 ° C. or higher.
（実施例９）
吸着する有機化合物をクエン酸から酒石酸に変更した以外は、実施例１と同様にして、Ａｇ−Ｐｄ触媒粒子（１）に、酒石酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ−Ｐｄ触媒粒子（１）１００重量部に対し約５重量部の酒石酸が吸着していた。
Example 9
Tartaric acid was adsorbed in Ag-Pd catalyst particles (1) in an aqueous solution in the same manner as in Example 1 except that the adsorbing organic compound was changed from citric acid to tartaric acid.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, about 5 parts by weight of tartaric acid was adsorbed with respect to 100 parts by weight of the Ag—Pd catalyst particles (1).
この試料を、空気中、１６０℃、常圧にて、１０分間、放置したところ、二酸化炭素と水がほぼ量論量、気体として発生した。残った試料の炭素成分の残存量を熱分析装置により確認したところ、炭素成分の残存は認められず、酒石酸が完全に酸化分解していることが確認された。
なお、通常の状態では、酒石酸は２０６℃から分解を開始するため、２０６℃以上の温度でないと分解しない。
When this sample was allowed to stand in air at 160 ° C. and normal pressure for 10 minutes, carbon dioxide and water were generated in a substantially stoichiometric amount as a gas. When the remaining amount of the carbon component in the remaining sample was confirmed by a thermal analyzer, no carbon component remained, and it was confirmed that tartaric acid was completely oxidatively decomposed.
In a normal state, tartaric acid starts to decompose at 206 ° C., so it does not decompose unless the temperature is 206 ° C. or higher.
（比較例１）
クエン酸水溶液にＡｇコロイド粒子を添加し、このＡｇコロイド粒子に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｇ粒子１００重量部に対し５重量部のクエン酸が吸着していた。
その後、熱分析装置を用いて、この試料を、空気中、常圧にて加熱し、クエン酸の酸化分解が始まる温度を求めた。その結果、３２０℃まで温度を上げないと、クエン酸の酸化分解反応が始まらないことが確認された。
(Comparative Example 1)
Ag colloidal particles were added to the citric acid aqueous solution, and citric acid was adsorbed on the Ag colloidal particles in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of Ag particles.
Thereafter, this sample was heated in air at normal pressure using a thermal analyzer, and the temperature at which oxidative decomposition of citric acid begins was determined. As a result, it was confirmed that the oxidative decomposition reaction of citric acid would not start unless the temperature was raised to 320 ° C.
（比較例２）
クエン酸水溶液にＰｄコロイド粒子を添加し、このＰｄコロイド粒子に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ｐｄ粒子１００重量部に対し５重量部のクエン酸が吸着していた。
その後、熱分析装置を用いて、この試料を、空気中、常圧にて加熱し、クエン酸の酸化分解が始まる温度を求めた。その結果、３００℃まで温度を上げないと、クエン酸の酸化分解反応が始まらないことが確認された。
(Comparative Example 2)
Pd colloidal particles were added to the citric acid aqueous solution, and citric acid was adsorbed on the Pd colloidal particles in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of the Pd particles.
Thereafter, this sample was heated in air at normal pressure using a thermal analyzer, and the temperature at which oxidative decomposition of citric acid begins was determined. As a result, it was confirmed that the oxidative decomposition reaction of citric acid would not start unless the temperature was raised to 300 ° C.
（比較例３）
クエン酸水溶液にＡｕコロイド粒子を添加し、このＡｕコロイド粒子に、クエン酸を、水溶液中にて吸着させた。
その後、遠心分離を施し、固形分を分離して採取し、風乾させた。
この乾燥した試料においては、Ａｕ粒子１００重量部に対し５重量部のクエン酸が吸着していた。
その後、熱分析装置を用いて、この試料を、空気中、常圧にて加熱し、クエン酸の酸化分解が始まる温度を求めた。その結果、３４０℃まで温度を上げないと、クエン酸の酸化分解反応が始まらないことが確認された。
(Comparative Example 3)
Au colloidal particles were added to the citric acid aqueous solution, and citric acid was adsorbed on the Au colloidal particles in the aqueous solution.
Then, it centrifuged and isolate | separated solid content and extract | collected and air-dried.
In this dried sample, 5 parts by weight of citric acid was adsorbed with respect to 100 parts by weight of Au particles.
Thereafter, this sample was heated in air at normal pressure using a thermal analyzer, and the temperature at which oxidative decomposition of citric acid begins was determined. As a result, it was confirmed that the oxidative decomposition reaction of citric acid would not start unless the temperature was raised to 340 ° C.
本発明の有機化合物分解触媒粒子は、有機化合物、特にカルボキシル基を有する有機化合物を２００℃以下の温度にて酸化分解することができ、しかも、白金に比べて安価な貴金属粒子を用いることができるものであるから、排ガス中に含まれる有機化合物を分解除去するための触媒として用いるのはもちろんのこと、その他の工業用触媒としても有用である。 The organic compound decomposition catalyst particles of the present invention can oxidize and decompose organic compounds, particularly organic compounds having a carboxyl group, at a temperature of 200 ° C. or lower, and can use precious metal particles that are less expensive than platinum. Therefore, it is useful not only as a catalyst for decomposing and removing organic compounds contained in exhaust gas, but also as other industrial catalysts.
Claims (5)
１つの粒子中に、金、銀、パラジウムの群から選択された２種以上の元素をそれぞれ５重量％以上含有してなることを特徴とする有機化合物分解触媒粒子。 Catalyst particles for decomposing an organic compound containing a carboxyl group at a temperature of 200 ° C. or lower,
An organic compound decomposition catalyst particle, wherein each particle contains 5% by weight or more of two or more elements selected from the group consisting of gold, silver and palladium.
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