JPH0640959B2 - Method for producing platinum-supporting porous gel - Google Patents
Method for producing platinum-supporting porous gelInfo
- Publication number
- JPH0640959B2 JPH0640959B2 JP2155464A JP15546490A JPH0640959B2 JP H0640959 B2 JPH0640959 B2 JP H0640959B2 JP 2155464 A JP2155464 A JP 2155464A JP 15546490 A JP15546490 A JP 15546490A JP H0640959 B2 JPH0640959 B2 JP H0640959B2
- Authority
- JP
- Japan
- Prior art keywords
- gel
- chloroplatinic acid
- platinum
- complex salt
- forming
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 20
- 150000004703 alkoxides Chemical class 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine compound Chemical class 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
- 239000011148 porous material Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000004964 aerogel Substances 0.000 description 3
- 238000005336 cracking 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000000463 material Substances 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
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-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
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 229920000642 polymer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011877 solvent mixture 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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。TECHNICAL FIELD The present invention relates to a method for producing a porous gel in which platinum is uniformly supported, and particularly to a method for producing a platinum catalyst porous gel.
従来、白金などの（貴）金属の担持はディップコーティ
ングが主な方法であった。しかし、白金粒子の分散はあ
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 so good, and there was a problem that segregation was likely to occur.
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、溶液によるディッ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。Further, when this is supported on an airgel such as silica or alumina, the dip coating with a solution causes cracking or 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 capable of uniformly dispersing platinum in an aerogel with high dispersion and yet producing a platinum-supporting porous gel without causing cracking or contraction in the aerogel. This is an issue.
本発明は、白金を担持した多孔質ゲルの製造方法におい
て、塩化白金酸を、塩化白金酸に対し０．１〜１０倍モ
ル量の、塩化白金酸と錯塩を形成する塩基との反応によ
り形成した塩化白金酸の錯塩として存在する状態で、金
属アルコキシドを含むゲル形成用原料を加水分解するこ
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 relates to a method for producing a platinum-supporting porous gel, wherein chloroplatinic acid is formed by reacting 0.1 to 10 times the molar amount of chloroplatinic acid with a base that forms a complex salt with chloroplatinic acid. The method for producing a platinum-supporting porous gel is characterized by hydrolyzing a gel-forming material containing a metal alkoxide in the state of existing as a complex salt of chloroplatinic acid.
本発明は、塩化白金酸をそれと錯塩を形成できる塩基に
より塩化白金酸の錯塩とした状態において金属アルコキ
シドを含むゲル形成用原料を加水分解することにより、
塩化白金酸−塩基錯塩をその生成ゲル中に均一に分散さ
せることができ、それによりＰｔを均一に担持した多孔
質ゲルを作成できる。The present invention, by hydrolyzing a gel-forming raw material containing a metal alkoxide in a state in which chloroplatinic acid is a complex salt of chloroplatinic acid with a base capable of forming a complex salt with it,
The chloroplatinic acid-base complex salt can be uniformly dispersed in the resulting gel, whereby a porous gel uniformly supporting Pt can be prepared.
本発明に使用できる塩化白金酸としては、H2PtCl6、H2P
tCl4等が挙げられる。Examples of chloroplatinic acid that can be used in the present invention include H 2 PtCl 6 and H 2 P.
Examples include tCl 4 and the like.
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。その錯塩の形成反
応は比較的早いので、金属アルコキシドを含むゲル形成
用原料の加水分解の反応に比しても、錯塩の状態をつく
る上に問題はない。The method and time of forming the chloroplatinic acid-base complex salt are not particularly limited as long as the above conditions are satisfied, and any means can be used. Further, the timing of adding the chloroplatinic acid and the base is not particularly limited as long as the above conditions are satisfied. Since the complex salt-forming reaction is relatively fast, there is no problem in forming the complex salt state compared to the hydrolysis reaction of the gel-forming raw material containing the metal alkoxide.
例えば、該加水分解前に該金属アルコキシドを含むゲル
形成用原料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 a gel-forming raw material containing the metal alkoxide before the hydrolysis and then the mixture is hydrolyzed, chloroplatinic acid and / or a base is further added 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.
塩化白金酸および塩基の金属アルコキシドを含むゲル形
成用原料への添加形態は、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 addition form to the gel-forming raw material containing a metal alkoxide of chloroplatinic acid and a base may be added by itself or dissolved in an organic solvent such as water or alcohol, but preferably water and 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ゲル形
成用原料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 70% by weight, preferably 0.1 to 15% by weight, based on the porous gel obtained by hydrolyzing the gel-forming raw material containing the metal alkoxide. It is a range.
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% chloroplatinic acid.
It is used in a 10-fold molar amount, preferably in a 1- to 2-fold molar amount. When the amount used is 0.1 times or less, a homogeneous gel cannot be obtained because the amount of chloroplatinic acid-base complex salt is extremely small. If the amount used is 10 times or more mol,
Gelation becomes too fast.
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 the base, if it is possible to form a complex salt with chloroplatinic acid,
Although not particularly limited, preferred examples include amine compounds such as pyridine, piperidine, piperazine, and pyrrolidine. Of these, pyridine is 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
ゲル形成用原料の中、金属アルコキシドとしては、Ｐｔ
を担持する多孔質ゲルを作成するためのゲルを生成でき
るものならばなんでもよく、特に制限がないが、例え
ば、一般式M(OR)n(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、iso−プロピル、ｎ−ブチル、sec−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、Al、Si、Zr、Ti、B、Ge、Be、Mg、Y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、B、Si、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。In the gel-forming raw material containing the metal alkoxide that is hydrolyzed in the present invention, the metal alkoxide is Pt.
Any material may be used as long as it can form a gel for supporting a porous gel, and is not particularly limited, for example, the general formula M (OR) n (M: metal or metalloid element, R: alkyl group, n is a valence of a metal or metalloid element), and R is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-
Butyl and the like are exemplified. Examples of the metal or metalloid element include Al, Si, Zr, Ti, B, Ge, Be, Mg and Y. Here, the semimetal means an element in the vicinity of the boundary with the metal element on the periodic table, and examples thereof include B, Si, Ge, As and the like. These metal alkoxides may be in the form of a hydrolyzable polymer metal alkoxide obtained by partially hydrolyzing these monomers in addition to the monomers of the above general formula.
該ゲル形成用原料には、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 possible to add a metal element component as a compound species other than the metal alkoxide to the gel-forming raw material.
Examples include the use of chlorides, nitrates, etc., which may or may not be hydrolyzable, but after formation of the porous gel:
It is preferable that components other than metal components do not remain as much as possible.
これら金属アルコキシドを含むゲル形成用原料を加水分
解反応に供すると共に重縮合せしめてゲルを得る方法と
しては、公知の手法を応用することが可能であり、該ゲ
ル形成用原料と水との混和性、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、塩化白金酸−塩基錯塩、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−プロパノール、iso−プロパノー
ル、sec−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。As a method for obtaining a gel by subjecting a gel-forming raw material containing these metal alkoxides to a hydrolysis reaction and polycondensation, a known method can be applied, and the gel-forming raw material and water are miscible. From the viewpoint of reaction, it is preferable to carry out in the presence of an organic solvent. As the organic solvent used here, chloroplatinic acid and a base, chloroplatinic acid-base complex salts, those which dissolve the mixture are preferable, and specifically, methanol, ethanol, n-propanol, iso-propanol, sec-butanol and the like. Alcohols represented by, aromatic hydrocarbons represented by toluene, benzene, xylene, etc., tetrahydrofuran, dimethylformamide,
Although carbon tetrachloride and the like are exemplified, alcohols having a relatively low boiling point such as methanol and ethanol are preferable.
金属アルコキシドを含むゲル形成用原料を加水分解する
前に該ゲル形成用原料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
−プロパノ−ルアミン、モノiso−プロパノ−ルアミ
ン、ジエタノールアミン、ジiso−プロパノ−ルアミ
ン、トリエタノールアミン、トリiso−プロパノ−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、マロン酸ジエチルな
どの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。Before hydrolyzing the gel-forming raw material containing the metal alkoxide, a compound that improves the hydrolysis by adding to the gel-forming raw material can be added. For example, as the compound, a compound capable of forming a complex with a metal alkoxide or the like can be given. For example, monoethanolamine, mono-n
-Alkanolamines such as propanolamine, monoiso-propanolamine, diethanolamine, diiso-propanolamine, triethanolamine, triiso-propanolamine, ethyl acetoacetate, methyl acetoacetate, ethyl malonate, malonic acid Examples include β-keto acid esters such as diethyl, and β-diketone compounds such as acetylacetone. These compounds are added in a molar amount of 0.5 to 2 times that of the compound capable of forming a complex such as 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。The amount of water used for the hydrolysis for forming a gel in the present invention varies depending on the kind of the hydrolyzable compound such as metal alkoxide, but is usually 0.3 to 0.3 to the hydrolyzable group of those compounds. 10-fold molar, preferably
It is in the range of 1 to 3 times by mole. The amount of water in this case includes the amount of water when chloroplatinic acid, a base or the like is used as an aqueous solution or a water / organic solvent mixed solution.
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。The method for drying the gel formed in the present invention is not particularly limited, and a conventionally known method 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。Specific examples include room temperature and normal pressure drying, supercritical drying and the like.
該超臨界乾燥には以下の２種が挙げられる。The supercritical drying includes the following two types.
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 CO2−ゲル溶媒混合系の超臨界乾燥条件下で乾燥 CO2−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H2PtCl6
を用いた例を説明するが、他の塩基についても同様の機
構が考えられえる。Drying gel solvent (eg alcohol) itself under supercritical drying conditions For ethanol; 243 ° C or higher, 63.8 atm or higher For methanol; 239.4 ° C or higher, 80.9 atm or higher CO 2 -gel solvent mixture Dry CO 2 -ethanol mixed system under supercritical drying conditions; 80 ° C or higher, 160 atm or higher [Function] Pyridine is used as a base and H 2 PtCl 6 is used as chloroplatinic acid.
Although an example using is explained, the same mechanism can be considered for other bases.
H2PtCl6はピリジンと反応し、安定な錯塩、即ち(C5H5N
H)2PtCl6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(C5H5N)2PtCl4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。H 2 PtCl 6 reacts with pyridine to give a stable complex salt, namely (C 5 H 5 N
H) 2 PtCl 6 is formed, and this complex salt is stably present in the gel. Moreover, since this complex salt changes to insoluble (C 5 H 5 N) 2 PtCl 4 that is difficult to elute in alcohol even at supercritical conditions at high temperatures, there is no heterogeneity due to the movement of platinum particles, and platinum particles in the gel body are eliminated. Can be more uniformly and highly dispersed.
また、ピリジンは塩基性であるため、酸性のH2PtCl6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。Since pyridine is basic, it can neutralize acidic H 2 PtCl 6 to promote gelation and strengthen the gel skeleton.
Al(OC4H9)3 sec１８ｇにＥＡＡ（アセト酢酸エチル）
７．９２５ｇを添加して１時間還流し、Al(OC4H9)3 sec
−ＥＡＡ複合体含有混合物を得た。Al (OC 4 H 9 ) 3 sec 18g EAA (ethyl acetoacetate)
7.925 g was added and refluxed for 1 hour. Al (OC 4 H 9 ) 3 sec
-A mixture containing EAA complex was obtained.
Si(OC2H5)4０．７２４５ｇとC2H5OH０．４ｇで薄めた水
を加えて部分加水分解した。これを前述のAl(OC4H9)3
sec−ＥＡＡ複合体含有混合物に加え、C2H5OH１６mlも
加えて０．５ｈ還流した。Partially hydrolyzed by adding water diluted with 0.7245 g of Si (OC 2 H 5 ) 4 and 0.4 g of C 2 H 5 OH. This is the above-mentioned Al (OC 4 H 9 ) 3
In addition to the sec- EAA complex-containing mixture, 16 ml of C 2 H 5 OH was also added, and the mixture was refluxed for 0.5 h.
次に、この溶液を氷水中で冷やし、水４．１４７ｇ、C2
H5OH４０ml、H2PtCl6０．５１９５ｇ、ピリジン０．７
７９ｇを混ぜたものを徐々に加えてゆき、加水分解を行
った。Next, this solution was cooled in ice water, and 4.147 g of water and C 2
H 5 OH 40 ml, H 2 PtCl 6 0.5195 g, pyridine 0.7
A mixture of 79 g 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/cm2、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 be gelated and aged. This wet gel is treated under supercritical conditions (2
The solvent was removed at 70 kg / cm 2 , 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H2PtCl6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、(NH4)2PtCl6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 H 2 PtCl 6 alone was added and hydrolyzed without using pyridine in Example, gelation did not occur even after 7 days. When ammonia was added to change the pH to basic, a salt of (NH 4 ) 2 PtCl 6 was precipitated. This disappeared during aging, but when it was dried under supercritical conditions, it became an aerogel with platinum much precipitated at 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してその錯塩を形
成させ、塩化白金酸−塩基錯塩の状態において金属アル
コキシドを含むゲル形成用原料を加水分解することによ
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 is for forming a gel containing a metal alkoxide in the state of a chloroplatinic acid-base complex salt by simply using a chloroplatinic acid and a base which forms a complex salt with the chloroplatinic acid without using a special apparatus. By hydrolyzing the raw material, platinum can be uniformly dispersed in the gel, and it is a method of producing a good porous gel that can prevent the gel from cracking and shrinking, and also in terms of economy and labor saving. Are better.
Claims (2)
いて、塩化白金酸を、塩化白金酸に対し０．１〜１０倍
モル量の、塩化白金酸と錯塩を形成する塩基との反応に
より形成した塩化白金酸の錯塩とした状態で、金属アル
コキシドを含むゲル形成用原料を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. A method for producing a porous gel carrying platinum, wherein chloroplatinic acid is reacted with 0.1 to 10 times the molar amount of chloroplatinic acid by a base forming a complex salt with chloroplatinic acid. A method for producing a platinum-supporting porous gel, comprising hydrolyzing a gel-forming raw material containing a metal alkoxide in a state of forming a complex salt of chloroplatinic acid.
ジン、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 platinum-supported porous material according to claim 1, wherein the base forming a complex salt with chloroplatinic acid is an amine compound selected from the group consisting of pyridine, piperidine, piperazine and pyrrolidine. Method for producing gel.
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 JPH0448932A (en) | 1992-02-18 |
| JPH0640959B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3285614B2 (en) * | 1992-07-30 | 2002-05-27 | 日本碍子株式会社 | Exhaust gas purification catalyst and method for producing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0448932A (en) | 1992-02-18 |
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