JPH0448932A - Preparation of porous gel having platinum supported thereon - Google Patents
Preparation of porous gel having platinum supported thereonInfo
- Publication number
- JPH0448932A JPH0448932A JP15546490A JP15546490A JPH0448932A JP H0448932 A JPH0448932 A JP H0448932A JP 15546490 A JP15546490 A JP 15546490A JP 15546490 A JP15546490 A JP 15546490A JP H0448932 A JPH0448932 A JP H0448932A
- Authority
- JP
- Japan
- Prior art keywords
- chloroplatinic acid
- gel
- porous gel
- base
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 amine compound Chemical class 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000004964 aerogel Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 6
- 239000000499 gel Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000352 supercritical drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、白金を均一に担持した多孔質ゲルの製造方法
、特に白金触媒多孔質ゲルの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a porous gel that uniformly supports platinum, particularly a method for producing a platinum-catalyzed porous gel.
従来、白金などの（貴）金属の担持はデイツプコーティ
ングが主な方法であった。しかし、白金粒子の分散：ま
あまり良くなく、偏析しやすい問題があった。Conventionally, dip coating has been the main method for supporting (noble) metals such as platinum. However, the dispersion of platinum particles was not very good, and there was a problem that they were easily segregated.
さらに、これをシリカ、アルミナなどのエアロゲルに担
持する場合、溶液によるデイツプコーティングでは乾燥
時に、表面張力による割れや収縮が起こり、エアロゲル
がやられてしまう。Furthermore, when supporting this on an airgel such as silica or alumina, deep coating with a solution causes cracking and shrinkage due to surface tension during drying, and the airgel is destroyed.
本発明は上記従来技術の欠点を解消し、白金をエアロゲ
ルに均一に高分散させ、なおかつ、エアロゲルに割れや
、収縮をおこさすことなく白金担持多孔質ゲルを製造で
きる方法を提供することを解決課題とするものである。The present invention solves the above-mentioned drawbacks of the prior art and provides a method for manufacturing a platinum-supported porous gel by uniformly and highly dispersing platinum in an airgel without causing cracking or shrinkage in the airgel. This is an issue to be addressed.
本発明は、白金を担持した多孔質ゲルの製造方法ニおい
て、金属アルコキシドを含む混合物を塩化白金酸および
塩化白金酸と錯塩を形成する塩化白金酸に対し０．１〜
１０倍モル量の塩基の存在下で加水分解することを特徴
とする白金を担持した多孔質ゲルの製造方法であり、こ
れにより、上記課題を解決できる。The present invention provides a method for producing a porous gel supporting platinum, in which a mixture containing a metal alkoxide is mixed with chloroplatinic acid and chloroplatinic acid that forms a complex salt with the chloroplatinic acid.
This is a method for producing a porous gel supporting platinum, which is characterized in that hydrolysis is carried out in the presence of 10 times the molar amount of a base, and thereby the above-mentioned problems can be solved.
本発明は、金属アルコキシドを含む混合物を塩化白金酸
およびこれと錯塩形成可能な塩基の存在下に加水分解し
、塩化白金酸−塩基錯塩を生成ゲル中に均一に分散させ
ることによりｐｔを均一に担持した多孔質ゲルが作成で
きる。In the present invention, a mixture containing a metal alkoxide is hydrolyzed in the presence of chloroplatinic acid and a base capable of forming a complex salt with the same, and the chloroplatinic acid-base complex salt is uniformly dispersed in the resulting gel, thereby uniformly dispersing pt. A supported porous gel can be created.
本発明に使用できる塩化白金酸としては、Ｈ２ＰｔＣＩ
、 、Ｈ２ＰｔＣＩ＜等が挙げられる。As the chloroplatinic acid that can be used in the present invention, H2PtCI
, , H2PtCI<, etc.
該塩化白金酸−塩基錯塩の形成法および形成時期は、上
記条件を満足すれば特に制限なく任意の手段を用いるこ
とができる。また、塩化白金酸と塩基の添加時期も、上
記条件を満たせば特に限定されない。The method and timing of forming the chloroplatinic acid-base complex salt are not particularly limited and any means can be used as long as the above conditions are satisfied. Furthermore, the timing of addition of chloroplatinic acid and base is not particularly limited as long as the above conditions are met.
例えば、該加水分解前に該金属アルコキシドを含む混合
物に塩化白金酸および／または塩基を添加して後、加水
分解しても、加水分解時に更に塩化白金酸および／また
は塩基を該混合物に添加してもよいが、好ましくは、加
水分解時に塩化白金酸と塩基を塩化白金酸−塩基錯塩の
形態で水と共に添加することが望ましい。For example, even if chloroplatinic acid and/or a base is added to the mixture containing the metal alkoxide before the hydrolysis, and then the mixture is hydrolyzed, chloroplatinic acid and/or the base is further added to the mixture during the hydrolysis. However, it is preferable to add chloroplatinic acid and a base together with water in the form of a chloroplatinic acid-base complex salt during hydrolysis.
塩化白金酸右よび塩基の金属アルコキシドを含む混合物
への添加形態は、それ自体を添加しても水またはアルコ
ール等の有機溶剤に溶解して添加してもよいが、好まし
くは、水および／または有機溶剤の溶液として添加され
る。The form of addition of chloroplatinic acid and a base to a mixture containing a metal alkoxide may be by adding it as such or by dissolving it in water or an organic solvent such as alcohol, but preferably water and/or Added as a solution in an organic solvent.
塩化白金酸の添加量は、金属アルコキシドを含む混合物
を加水分解して得られる多孔質ゲルに対して０．０１〜
７０重量％、好ましくは、０．１〜１５重量％となるよ
うな範囲である。The amount of chloroplatinic acid added is 0.01 to 0.01 to a porous gel obtained by hydrolyzing a mixture containing metal alkoxide.
The range is 70% by weight, preferably 0.1 to 15% by weight.
本発明に用いられる塩基は、塩化白金酸に対し０．１〜
１０倍モル量、好ましくは、１〜２倍モル量使用される
。この使用量が０． １倍モル以下であると、塩化白金
酸−塩基錯塩の量が極端に少ないため、均質なゲルが得
られない。また、同使用量が１０倍モル以上であると、
ゲル化が速くなりすぎてしまう。The base used in the present invention is 0.1 to 0.1 to chloroplatinic acid.
It is used in a 10-fold molar amount, preferably in a 1 to 2-fold molar amount. This usage amount is 0. If the amount is less than 1 mole, the amount of chloroplatinic acid-base complex salt is extremely small, making it impossible to obtain a homogeneous gel. In addition, if the same amount used is 10 times the mole or more,
Gelation will occur too quickly.
塩基としては、塩化白金酸と錯塩を形成可能であれば、
特に限定されないが、好ましくは、ピリジン、ピペリジ
ン、ピペラジン、ピロリジン等のアミン化合物が挙げら
れ、この中でも特にピリジンが好ましい。As a base, if it can form a complex salt with chloroplatinic acid,
Although not particularly limited, preferred examples include amine compounds such as pyridine, piperidine, piperazine, and pyrrolidine, with pyridine being particularly preferred.
本発明において加水分解される金属アルコキシドを含む
混合物の白金属アルコール類としては、特に制限はない
が、例えば、一般式Ｍ（ＯＲ）ｈ（Ｍ：金属または半金
属元素、Ｒ；アルキル基、ｎ：金属または半金属元素の
価数）で表されるものであり、Ｒとしては、メチル、エ
チル、ｎ−プロピル、１ｓｏ−プロピノペローブチル、
５ｅｃ−ブチル、ｔｅｒｔ−ブチル等が例示される。ま
た金属または半金属元素としては、＾ｌ、Ｓｉ、Ｚｒ５
ＴｉＳＢ ５ＧｅＳＢｅ、Ｍｇ５Ｙ等が例示される。こ
こで、半金属とは、周期律表上で金属元素との境界付近
の元素を意味し、ａ、Ｓｌ、Ｇｅ、 Ａｓ等が例示され
る。これら金属アルコキシドは、上記一般式自体の単量
体に加えこれら単量体を部分加水分解して得られる加水
分解可能な多量体金属アルコキシドの形態でもよい。There are no particular limitations on the platinum metal alcohols in the mixture containing metal alkoxides to be hydrolyzed in the present invention, but examples include general formula M(OR)h (M: metal or metalloid element, R: alkyl group, n : the valence of the metal or metalloid element), and R is methyl, ethyl, n-propyl, 1so-propinoperbutyl,
Examples include 5ec-butyl and tert-butyl. In addition, as metal or metalloid elements, ^l, Si, Zr5
Examples include TiSB 5GeSBe, Mg5Y, and the like. Here, the semimetal means an element near the boundary with a metal element on the periodic table, and examples include a, Sl, Ge, and As. These metal alkoxides may be in the form of a hydrolyzable multimeric metal alkoxide obtained by partially hydrolyzing these monomers in addition to the monomers of the above general formula.
該混合物には、上記各種金属アルコキシドに加えて、金
属アルコキシド以外の化合物種として金属元素成分を添
加することも可能であり、金属単体、酢酸塩、塩化物、
硝酸塩等の使用が例示され、これらは、加水分解可能で
もそうでなくともよいが、多孔質ゲル形成後、金属成分
以外の成分が極力残留しないものがよい。In addition to the above-mentioned various metal alkoxides, it is also possible to add metal element components to the mixture as compound species other than metal alkoxides, such as simple metals, acetates, chlorides,
An example is the use of nitrates, which may or may not be hydrolyzable, but it is preferable that components other than metal components remain as little as possible after the porous gel is formed.
これら金属アルコキシドを含む混合物を加水分解反応に
供すると共に重縮合ゼし杓でゲルを得る方法としては、
公知の手法を応用することが可能であり、該混合物と水
との混和性、反応の面から有機溶媒存在下で行うのが好
ましい。ここで用いる有機溶媒としては、塩化白金酸お
よび塩基、該混合物を溶解するものが好ましく、具体的
にはメタノール、エタノール、ｎ−プロパツール、ｉｓ
ｏ −プロパツール、５ｅｃ−ブタノール等に代表され
るアルコール類、トルエン、ベンゼン、キシレン等に代
表される芳香族系炭化水素、テトラヒドロフラン、ジメ
チルホルムアミド、四塩化炭素等が例示されるが、メタ
ノール、エタノール等の比較的沸点の低いアルコール類
が好ましい。A method of subjecting a mixture containing these metal alkoxides to a hydrolysis reaction and polycondensation to obtain a gel using a ladle is as follows:
It is possible to apply known methods, and it is preferable to carry out the reaction in the presence of an organic solvent from the viewpoint of the miscibility of the mixture with water and the reaction. The organic solvent used here is preferably one that dissolves chloroplatinic acid and a base, and specifically, methanol, ethanol, n-propanol, is
Examples include alcohols such as o-propertool and 5ec-butanol, aromatic hydrocarbons such as toluene, benzene, and xylene, tetrahydrofuran, dimethylformamide, and carbon tetrachloride, but methanol and ethanol Alcohols with relatively low boiling points, such as, are preferred.
金属アルコキシドを含む混合物を加水分解する前に該混
合物に添加して加水分解を改善する化合物を添加するこ
とができる。例えば、該化合物として、金属アルコキシ
ド等と複合体を形成可能な化合物が挙げられ、例示すれ
ば、モノエタノールアミン、モノｎ−プロパツールアミ
ン、モノｌｓ。Compounds can be added to the mixture containing metal alkoxides before the mixture is hydrolyzed to improve hydrolysis. For example, such compounds include compounds capable of forming complexes with metal alkoxides and the like, such as monoethanolamine, mono-n-propaturamine, and mono-ls.
−フロパノールアミン、ジェタノールアミン、ジ１ｓｏ
−プロパツールアミン、トリエタノールアミン、トリ１
ｓｏ−プロパツールアミンなどのアルカノールアミン、
アセト酢酸エチル、アセト酢酸メチル、マロン酸エチル
、マロン酸シエチルナトノβケト酸エステル、アセチル
アセトン等のβジケトン化合物が挙げられる。これら化
合物は、金属アルコキシド等の複合体形成可能な化合物
に対し０．５〜２倍モル添加される。-furopanolamine, jetanolamine, di-1so
-Propertoolamine, triethanolamine, tri-1
alkanolamines such as so-propaturamine,
Examples thereof include β-diketone compounds such as ethyl acetoacetate, methyl acetoacetate, ethyl malonate, ethyl malonate natono β-keto acid ester, and acetylacetone. These compounds are added in a molar amount of 0.5 to 2 times the amount of a compound capable of forming a complex such as a metal alkoxide.
本発明においてゲル形成のための加水分解に用いられる
水の量は、金属アルコキシド等の加水分解可能な化合物
の種類によって異なるが、通常、それら化合物の加水分
解可能な基に対して０．３〜１０倍モル、好ましくは、
１〜３倍モルの範囲である。この場合の水の量は、塩化
白金酸、塩基等を水溶液もしくは水・有機溶媒混合溶液
として用いた場合のその水の量も含めたものである。In the present invention, the amount of water used for hydrolysis to form a gel varies depending on the type of hydrolyzable compound such as metal alkoxide, but is usually 0.3 to 0.3 to 10 times molar, preferably
The range is 1 to 3 times the mole. The amount of water in this case also includes the amount of water when chloroplatinic acid, a base, etc. are used as an aqueous solution or a mixed solution of water and an organic solvent.
本発明において形成されたゲルの乾燥法にも特に制限は
なく、従来公知の方法が適用できる。There is no particular restriction on the method of drying the gel formed in the present invention, and conventionally known methods can be applied.
具体的には、常温常圧乾燥、超臨界乾燥等が例示される
。Specifically, drying at normal temperature and pressure, supercritical drying, etc. are exemplified.
該超臨界乾燥には以下の２種が挙げられる。The following two types of supercritical drying are mentioned.
■ ゲル溶媒（例えば、アルコール）そのものの超臨界
乾燥条件下で乾燥
エタノールの場合；２４３℃以上、６３．８気圧以上
メタノールの場合；２３９．４℃以上、８０゜９気圧以
上
■ ＣＯ□−ゲル溶媒混合系の超臨界乾燥条件下で乾燥
Ｃ０２−エタノール混合系の場合；８０℃以上、１６０
気圧以上
〔作用〕
塩基としてピリジンを用い、塩化白金酸としてＨ，Ｐｔ
Ｃｌ６を用いた例を説明するが、他の塩基にっいても同
様の機構が考えられえる。■ Dry under the supercritical drying conditions of the gel solvent (e.g. alcohol) itself; For ethanol; 243°C or higher, 63.8 atm or higher For methanol; 239.4°C or higher, 80° or higher 9 atm ■ CO□-Gel Dry under supercritical drying conditions for solvent mixed systems; For CO2-ethanol mixed systems: 80°C or higher, 160°C
Atmospheric pressure or higher [action] Using pyridine as the base, H, Pt as chloroplatinic acid
Although an example using Cl6 will be explained, a similar mechanism can be considered for other bases as well.
）１２Ｐｔｃｌ、はピリジンと反応し、安定な錯塩、即
ち（ｔ’５Ｈ５Ｎ）Ｉ） 、ＰｔＣ］、を形成し、この
錯塩は安定にゲル中に存在する。しかも、この錯塩は超
臨界状態でも高温でアルコール中に溶出しにくい不溶の
（ＣｓＨｓＮ） ２Ｐ ｔｃ１＊に変化するので、白金
粒子の移動による不均一化もなくなり、ゲル体に白金粒
子をより均一に高分散させることができる。)12Ptcl, reacts with pyridine to form a stable complex salt, namely (t'5H5N)I) , PtC], which stably exists in the gel. Moreover, this complex salt changes to insoluble (CsHsN) 2P tc1* that is difficult to dissolve in alcohol at high temperatures even in a supercritical state, so there is no unevenness due to the movement of platinum particles, and the platinum particles are more uniformly distributed in the gel body. Can be highly dispersed.
また、ピリジンは塩基性であるため、酸性の）１．Ｐｔ
ｃｌ、を中和して、ゲル化を促進するとともにゲル骨格
の強化もできる。In addition, since pyridine is basic, it is also acidic). Pt
By neutralizing Cl, it is possible to promote gelation and strengthen the gel skeleton.
Ａｌ（ＯＣ４）ＩＳ）３”ｃｌ ８ ｇ ニＥ Ａ Ａ
（７（！ト酢酸エチル）７．９２５ｇを添加して１時
間還流し、＾１（ＱＣ４Ｈ，）、”’ −ＥＡＡ複合体
含有混合物を得た。Al(OC4)IS) 3”cl 8 g NiE A A
(7.925 g of ethyl triacetate) was added and the mixture was refluxed for 1 hour to obtain a mixture containing ^1(QC4H,),''-EAA complex.
５ｌ（ＯＣＪｓ）４ｏ、 ７２４５ ｇとＣＪｓＯ）
１０ 、 ４ ｇで薄めた水を加えて部分加水分解した
。これを前述のＡＩ （ＯＣ４Ｈｓ） ３”ｃＥ Ａ
Ａ複合体含有混合物に加え、ＣＪｓ［ｌＨｌ ６ ｄも
加えて０．５ね還流した。5l (OCJs) 4o, 7245g and CJsO)
Partial hydrolysis was carried out by adding 10.4 g of diluted water. This is the aforementioned AI (OC4Hs) 3”cE A
In addition to the mixture containing the A complex, CJs[lHl 6 d was also added and the mixture was refluxed for 0.5 minutes.
次に、この溶液を氷水中で冷やし、水４．１４７ ｇ、
Ｃ，Ｉ（、ＯＨ４０ｍｊ！、 ｕ、ＰｔＣ１ｇ ｏ
、 ５１９５ ｇ。Next, this solution was cooled in ice water, 4.147 g of water,
C, I(, OH40mj!, u, PtC1g o
, 5195 g.
ピリジン０．７７９ｇを混ぜたものを徐々に加えてゆき
、加水分解を行った。A mixture of 0.779 g of pyridine was gradually added to carry out hydrolysis.
このできたゾルを６０℃に７日間程保ち、ゲル化させる
と共に熟成を行った。この湿潤ゲルを超臨界条件下（２
７０ｋｇ／ｃａｆ、 ２７０℃）で溶媒を除き、白金を
均一に分散させたエアロゲルを得た。The resulting sol was kept at 60° C. for about 7 days to gel and age. This wet gel was processed under supercritical conditions (2
The solvent was removed at 70 kg/caf (270° C.) to obtain an airgel in which platinum was uniformly dispersed.
比較例
実施例においてピリジンを使用せず８２ＰｔＣ１，のみ
を添加して加水分解した場合は、７日間してもゲル化し
なかった。また、ｐＨを塩基性に変えるためにアンモニ
アを添加したところ、（Ｎｕ、）ａＰｔｃＩｓの塩が沈
澱してしまった。これは熟成中にみえなくなったが、超
臨界条件で乾燥すると白金が底の方に多く沈澱したよう
なエアロゲルになってしまった。Comparative Example When pyridine was not used and only 82PtC1 was added for hydrolysis, gelation did not occur even after 7 days. Furthermore, when ammonia was added to make the pH basic, the (Nu,)aPtcIs salt precipitated. This disappeared during ripening, but when dried under supercritical conditions, it became an aerogel with more platinum precipitated toward the bottom.
本発明は、特殊な装置を使用することなく単に塩化白金
酸とこれと錯塩を形成する塩基を使用することのみによ
って、白金をゲルに均一に分散することができ、かつゲ
ルの割れや収縮を防止できる良好な多孔質ゲルを製造す
る方法であり、また、経済性、省力性においても優れて
いる。The present invention enables platinum to be uniformly dispersed in a gel by simply using chloroplatinic acid and a base that forms a complex salt with it, without using special equipment, and prevents cracking and shrinkage of the gel. This is a method for producing a good porous gel that can prevent the above problems, and is also excellent in terms of economy and labor saving.
（ほか３名）(3 others)
Claims (2)
金属アルコキシドを含む混合物を塩化白金酸および塩化
白金酸と錯塩を形成する塩化白金酸に対し０．１〜１０
倍モル量の塩基の存在下で加水分解することを特徴とす
る白金を担持した多孔質ゲルの製造方法。(1) In a method for producing a porous gel supporting platinum,
0.1 to 10% of a mixture containing a metal alkoxide to chloroplatinic acid and chloroplatinic acid that forms a complex salt with chloroplatinic acid.
A method for producing a porous gel supporting platinum, which is characterized by hydrolysis in the presence of double the molar amount of a base.
ピペリジン、ピペラジン、ピロリジンからなる群から選
択されるアミン化合物であることを特徴とする請求項１
記載の白金を担持した多孔質ゲルの製造方法。(2) The base that forms a complex salt with chloroplatinic acid is pyridine,
Claim 1 characterized in that it is an amine compound selected from the group consisting of piperidine, piperazine, and pyrrolidine.
A method for producing a porous gel supporting platinum as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2155464A JPH0640959B2 (en) | 1990-06-15 | 1990-06-15 | Method for producing platinum-supporting porous gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2155464A JPH0640959B2 (en) | 1990-06-15 | 1990-06-15 | Method for producing platinum-supporting porous gel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0448932A true JPH0448932A (en) | 1992-02-18 |
| JPH0640959B2 JPH0640959B2 (en) | 1994-06-01 |
Family
ID=15606626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2155464A Expired - Lifetime JPH0640959B2 (en) | 1990-06-15 | 1990-06-15 | Method for producing platinum-supporting porous gel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640959B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439865A (en) * | 1992-07-30 | 1995-08-08 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and process for production thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6161645A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using alumina as carrier |
| JPS6161646A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using titania as carrier |
| JPS6161647A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using zirconia as carrier |
| JPS6161644A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using silica as carrier |
-
1990
- 1990-06-15 JP JP2155464A patent/JPH0640959B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6161645A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using alumina as carrier |
| JPS6161646A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using titania as carrier |
| JPS6161647A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using zirconia as carrier |
| JPS6161644A (en) * | 1984-09-03 | 1986-03-29 | Agency Of Ind Science & Technol | Preparation of porous and highly dispersed metallic catalyst using silica as carrier |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439865A (en) * | 1992-07-30 | 1995-08-08 | Ngk Insulators, Ltd. | Catalyst for exhaust gas purification and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0640959B2 (en) | 1994-06-01 |
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