JPS6319217B2 - - Google Patents
Info
- Publication number
- JPS6319217B2 JPS6319217B2 JP57228546A JP22854682A JPS6319217B2 JP S6319217 B2 JPS6319217 B2 JP S6319217B2 JP 57228546 A JP57228546 A JP 57228546A JP 22854682 A JP22854682 A JP 22854682A JP S6319217 B2 JPS6319217 B2 JP S6319217B2
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- catalyst
- hydrosol
- metal
- rhodium
- 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
Links
- 229910000510 noble metal Inorganic materials 0.000 claims description 54
- 239000003054 catalyst Substances 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 ruthenium Chemical class 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- CKQAOGOZKZJUGA-UHFFFAOYSA-N 1-nonyl-4-(4-nonylphenoxy)benzene Chemical compound C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 CKQAOGOZKZJUGA-UHFFFAOYSA-N 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008131 herbal destillate Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は、高い触媒活性を示す新規な貴金属ヒ
ドロゾル触媒の製造方法及び担持型貴金属触媒の
製造方法に関するものである。
金属触媒として、これまでに多くの形態が考え
出されているが、そのうちでも金属微粒子を含む
担持型触媒は、反応後の回収が容易であると同時
に、金属比表面積が大きく、触媒となる金属の使
用量を大幅に低減できることから、価格の高い貴
金属触媒に特に適している。担持型貴金属触媒に
ついては、従来からの製法として、活性炭やシリ
カゲル、ケイソウ土といつた比表面積の比較的大
きな不活性固体に、触媒となる貴金属の塩を含浸
ないし吸着させ、次いで、これを分子状水素など
の適当な還元剤で処理することにより貴金属塩を
還元して担体表面上で貴金属微粒子を形成させる
方法が知られている。しかし、この方法では、担
体上の貴金属塩を全て貴金属微粒子に変換するた
めに、相当高温下で還元反応を行う必要があり、
その場合、貴金属微粒子の二次的な成長が起こる
ため、その粒度分布が広がりがちで、触媒活性の
再現性についても、しばしば問題が生じる。ま
た、担体表面上の貴金属塩の密度が低い場合、一
般に還元が困難となり、貴金属の種類によつては
低担持率の担持触媒が実際上調製できないことも
ある。
この他の金属触媒の形態として、液体中に、コ
ロイド粒子と呼ばれる数100オングストローム又
はこれ以下の粒径の金属微粒子が均一に分散した
金属ゾルがあり、特に貴金属について多くの種類
が知られている。これは、調製が容易であるう
え、金属塩の還元反応が溶液中で穏和な条件下に
行われるため、粒度分布の狭い金属微粒子が得ら
れ、その触媒活性の再現性が良好である点で優れ
ている。金属ゾルは外見上完全に透明な液体であ
り、通常、液相反応の触媒として用いられるが、
反応後に触媒と生成物を分離する時、固体触媒の
ようなろ過による方法は適用できない。それで例
えば、生成物を留出させて分離することを考える
と、金属ゾルがこの時凝集沈殿を起さないこと、
すなわち、高温下での分散の安定性が要求される
ことになる。金属ゾルには、その分散状態を安定
化させるため保護コロイドと呼ばれる可溶性高分
子が添加されることが多いが、水を分散媒とする
金属ヒドロゾルの場合、その分散状態を高温下で
も安定に保つには、かなり多量の保護コロイド高
分子の添加が必要であり、この高分子が、今度は
触媒反応に対し抑制剤として働くことになる。こ
の他の解決法として、金属ゾル中の金属コロイド
粒子を適当な不溶性固体上に担持することができ
れば、金属ゾル触媒同様調製が容易で触媒活性の
再現性が良く、同時にろ過などの簡単な操作で容
易に回収し得る優れた担持型金属触媒が得られる
と期待される。このような観点から考え出され
た、金属ゾルからの担持型触媒の調製法がいくつ
かあるが、この場合、保護コロイド高分子によつ
て保護された金属ゾルはこの用途に適さず、保護
剤を用いないで、その代り金属含有率を極めて低
く抑えた金属ヒドロゾルを使用せざるを得ない。
このゾルは準安定とでもいうべき状態で、比較的
低温でも徐々に凝集が進むことと、扱う金属ヒド
ロゾルが大量となることなどが、この方法の難点
である。また、保護コロイド不在下では低濃度で
もヒドロゾルを形成し得ない金属、例えば、ルテ
ニウムの担持型触媒の調製には適用できない。
本発明者らは、従来触媒のこのような難点を克
服し、より優れた性能の貴金属触媒を容易に調製
できる方法を確立すべく鋭意検討を重ねた結果、
界面活性剤により保護された貴金属ヒドロゾル
が、高い触媒活性を示すと同時に、貴金属含有率
が高い場合もその分散状態が安定で、高温下にお
いても全く凝集を起こさないこと、及び、これに
含まれる貴金属コロイド粒子が特定の担体物質の
表面に効率よく吸着され、その結果得られる担持
型貴金属触媒もまた高い触媒活性を示すことを見
出した。本発明は、これらの知見に基づいて成す
に至つたものである。
すなわち、本発明は、ロジウム、パラジウム、
白金、ルテニウムの中から選ばれた貴金属の塩を
水溶液とし、さらに、陽イオン性、陰イオン性又
は非イオン性界面活性剤を溶解した後に、還元処
理することを特徴とする貴金属ヒドロゾル触媒の
製造方法及び、この貴金属ヒドロゾルを難溶性又
は不溶性の担体物質と接触させて、これに含まれ
る貴金属コロイド粒子を担体表面上に担持させる
ことを特徴とする担持型貴金属触媒の製造方法を
提供するものである。
本発明方法において原料として用いられる貴金
属塩は、当該貴金属の水溶性の塩化物、硝酸塩な
どであり、例えば、塩化ロジウム（）、塩化パ
ラジウム（）、塩化白金酸、塩化ルテニウム
（）などが好適である。
本発明方法においては、貴金属ヒドロゾルの保
護物質として界面活性剤を用いることが必要であ
るが、この界面活性剤としては、例えば、ステア
リルトリメチルアンモニウムクロリド、ヘキサデ
シルトリメチルアンモニウムブロミド、ヘキサデ
シルピリジニウムクロリドなどの陽イオン性界面
活性剤、ドデシル硫酸ナトリウム、ドデシルベン
ゼンスルホン酸ナトリウムなどの陰イオン性界面
活性剤、ポリエチレングリコールモノ−ｐ−ノニ
ルフエニルエーテルなどの非イオン性界面活性剤
をあげることができる。
また、還元処理の方法としては、水素化ホウ素
ナトリウム、水素化ホウ素カリウムなどのアルカ
リ金属水素化ホウ素塩の他、ヒドラジン、ホルム
アルデヒドなどの水溶性還元性物質を用いる貴金
属塩の還元について公知の方法がとられる。
本発明方法を実施するには、所定の貴金属塩及
び界面活性剤を水に溶解し、かくはん下に、０℃
ないし100℃、通常は室温において還元剤又は還
元剤の水溶液を加える。こうして、貴金属ヒドロ
ゾルが、強く着色した透明な液体として得られ
る。この際、原料となる貴金属塩は、水溶液中で
の濃度が0.01〜30ｍmol／の範囲になるように
用いられ、界面活性剤は、水溶液中の濃度が
0.001〜５％の範囲になるように用いられる。ま
た、還元剤は、原料の貴金属塩に対し、等モル以
上用いられるのが望ましい。得られた貴金属ヒド
ロゾルは、そのまま均一液相触媒として、水溶液
反応に供することができる。
本発明においては、さらに、担体として難溶性
又は不溶性の物質が用いられる。担持処理は、貴
金属ヒドロゾル中に、担体となる物質を懸濁させ
てかくはんすることにより行われる。この時、担
体表面が着色するに従つて貴金属ゾルの色は退色
し、これが無色になることで担持が完了したこと
を確認できる。貴金属コロイド粒子のヒドロゾル
から担体への移行が遅い場合には、適宜温度を上
昇させてこれを早めることができる。担持処理に
要する時間は、大部分の場合数分以内であり、最
も遅い場合でも、１時間以内に完了する。このよ
うにして貴金属コロイド粒子を担持した固体触媒
が得られる。
担体として用いられる物質としては、まず、水
に対し難溶又は不溶である、金属の水酸化物、酸
化物、フツ化物、炭酸塩、硫酸塩、リン酸塩をあ
げることができ、具体的には、水酸化マグネシウ
ム、酸化マグネシウム、フツ化マグネシウム、炭
酸マグネシウム、水酸化カルシウム、フツ化カル
シウム、炭酸カルシウム、硫酸カルシウム、リン
酸カルシウム、炭酸バリウム、硫酸バリウムなど
のアルカリ土類金属塩の他、水酸化アルミニウ
ム、酸化チタン、酸化鉄（）、四三酸化鉄、酸
化銅（）、水酸化銅（）、酸化亜鉛、炭酸亜
鉛、酸化ジルコニウムなどをあげることができ
る。この他、イオン交換樹脂、活性炭、粉砕した
石炭、活性白土なども担体として用いられる。な
お、その形態は100meshより細かい粉末状が好ま
しいが、貴金属の担持率が低い場合には、これ以
外の例えば、粒状のものや成形品を用いることも
可能である。担体物質は、形成される貴金属コロ
イド粒子の20〜10000倍重量、好ましくは50〜500
倍重量が用いられる。
得られた担持型貴金属触媒を含む懸濁液は、そ
のままで水溶液の液相反応に供することもできる
が、通常は静置又は遠心分離により沈降させ、又
はろ過して該固体触媒を分散し、水又はアルコー
ルなどで洗浄後、乾燥させて使用する。
本発明方法により得られる貴金属ヒドロゾルの
第一の特徴は、これが非常に高い触媒活性を有す
ることである。一例として、オレフインの水素化
触媒として用いた場合の単位貴金属あたりの比較
では、本発明方法によるロジウムヒドロゾルは、
市販の活性炭担持ロジウム触媒の５倍以上の活性
を示す。第二の特徴は、分散状態の高い安定性に
あり、例えば常圧下で長時間沸騰させた後でも、
濁り又は沈殿は全く認められず、完全に透明な状
態を保ち触媒活性も低下しない。これに対し、例
えばポリビニルピロリドンを保護物質として使用
した貴金属ヒドロゾルは、調製直後に既に少量の
濁りが認められるうえ、沸騰などの加熱処理によ
り徐々に濁りが増加し触媒活性も低下する。
本発明方法により得られる担持型貴金属触媒も
また、高い触媒活性を示す点に特徴があり、担持
型ロジウム触媒の例でいえば、単位ロジウム当り
の比較で、界面活性剤を用いないロジウムヒドロ
ゾルから得られる担持触媒の２倍以上の触媒活性
を示す。この他、貴金属ヒドロゾルに対し、これ
と接触させる担体の使用量を増加させることによ
り、容易に低い担持率の貴金属触媒が得られるこ
とも本発明方法の特徴である。
本発明によれば、極めて微細な貴金属コロイド
粒子を含む貴金属ヒドロゾル触媒及び貴金属コロ
イド粒子を担持した固体触媒が容易に再現性よく
得られ、これら貴金属触媒はいずれも高い触媒活
性を示し、液相又は気相の広い範囲の触媒反応に
使用できる。
次に、実施例により本発明をさらに詳細に説明
する。
実施例 １
塩化ロジウム（）（RhCl3・3H2O）50μmol
及びポリエチレングリコールモノ−ｐ−ノニルフ
エニルエーテル（ポリエチレングリコール部分の
重合度＝10）10mgを純水95mlに溶解し、これに、
かくはん下、水素化ホウ素ナトリウム（NaBH4）
200μmolの水溶液５mlを滴下した。淡橙色の水溶
液は、滴下の途中に黒かつ色に急変し、目的のロ
ジウムヒドロゾルが得られた。このロジウムヒド
ロゾル0.4ml（ロジウムを0.2μｇ−atom含む）を
水素雰囲気中で、あらかじめアルゴン下で還流し
て酸素を除いた純水20ml中に、ヒドロゾル調製に
用いた界面活性剤、すなわちポリエチレングリコ
ールモノ−ｐ−ノニルフエニルエーテル２mgを溶
解した溶液で希釈し、さらに30℃、１気圧の水素
下でかくはんしながらアクリルアミド0.25ｍmol
の水溶液１mlを滴下すると水素の吸収が始まり、
プロピオンアミドが生成した。
水素吸収初速度は1.36mol／sec・ｇ−atomRh
であり、反応は約20分で完了した。
実施例 ２
実施例１と同様の操作により、原料となる貴金
属塩、界面活性剤及び還元剤を変えて貴金属ヒド
ロゾルを調製した。こうして得られた貴金属ヒド
ロゾルによる、水溶液中、30℃、１気圧水素下に
おけるアクリルアミドの水素化初速度を次表に示
す。
The present invention relates to a method for producing a novel noble metal hydrosol catalyst that exhibits high catalytic activity, and a method for producing a supported noble metal catalyst. Many forms of metal catalysts have been devised so far, but among them, supported catalysts containing fine metal particles are easy to recover after the reaction, have a large metal specific surface area, and are suitable for use with metals that serve as catalysts. It is particularly suitable for expensive precious metal catalysts because it can significantly reduce the amount of metal used. The conventional manufacturing method for supported precious metal catalysts is to impregnate or adsorb a precious metal salt that will serve as a catalyst into an inert solid with a relatively large specific surface area, such as activated carbon, silica gel, or diatomaceous earth. A method is known in which noble metal salts are reduced by treatment with a suitable reducing agent such as hydrogen to form noble metal fine particles on the surface of a carrier. However, in this method, in order to convert all the noble metal salts on the carrier into noble metal fine particles, it is necessary to carry out a reduction reaction at a considerably high temperature.
In this case, since secondary growth of noble metal fine particles occurs, the particle size distribution tends to widen, and problems often occur with respect to the reproducibility of catalyst activity. Furthermore, when the density of the noble metal salt on the surface of the carrier is low, reduction is generally difficult, and depending on the type of noble metal, it may not be possible to actually prepare a supported catalyst with a low loading rate. Another form of metal catalyst is metal sol, in which fine metal particles called colloidal particles with a particle size of several hundred angstroms or less are uniformly dispersed in a liquid, and many types are known, especially for noble metals. . This method is easy to prepare, and since the reduction reaction of the metal salt is carried out in a solution under mild conditions, fine metal particles with a narrow particle size distribution can be obtained, and the reproducibility of the catalytic activity is good. Are better. Metal sol is an apparently completely transparent liquid and is usually used as a catalyst for liquid phase reactions.
When separating the catalyst and products after the reaction, filtration methods such as those using solid catalysts cannot be applied. So, for example, when considering distilling and separating the product, it is important to make sure that the metal sol does not coagulate and precipitate at this time.
In other words, stability of dispersion at high temperatures is required. A soluble polymer called a protective colloid is often added to metal sol to stabilize its dispersion state, but in the case of metal hydrosols that use water as a dispersion medium, the dispersion state remains stable even at high temperatures. requires the addition of fairly large amounts of protective colloid polymers, which in turn act as inhibitors for the catalytic reaction. As another solution, if the metal colloid particles in the metal sol can be supported on a suitable insoluble solid, it is easy to prepare like a metal sol catalyst, has good reproducibility of catalytic activity, and at the same time allows simple operations such as filtration. It is expected that an excellent supported metal catalyst that can be easily recovered will be obtained. There are several methods of preparing supported catalysts from metal sol that have been devised from this perspective, but in this case, metal sol protected by a protective colloid polymer is not suitable for this purpose, and the protective agent is not suitable for this purpose. Instead, a metal hydrosol with an extremely low metal content must be used.
The disadvantages of this method include that this sol is in a state that can be called metastable, and that aggregation progresses gradually even at relatively low temperatures, and that a large amount of metal hydrosol must be handled. Furthermore, it cannot be applied to the preparation of supported catalysts for metals, such as ruthenium, which cannot form hydrosols even at low concentrations in the absence of protective colloids. The inventors of the present invention have conducted extensive studies to overcome these difficulties of conventional catalysts and to establish a method for easily preparing noble metal catalysts with superior performance.
The noble metal hydrosol protected by a surfactant exhibits high catalytic activity, and at the same time, its dispersion state is stable even when the precious metal content is high, and it does not aggregate at all even at high temperatures, and this includes: It has been found that noble metal colloid particles are efficiently adsorbed on the surface of a specific carrier material, and the resulting supported noble metal catalyst also exhibits high catalytic activity. The present invention has been achieved based on these findings. That is, the present invention provides rhodium, palladium,
Production of a noble metal hydrosol catalyst, which is characterized in that a salt of a noble metal selected from platinum and ruthenium is made into an aqueous solution, and then a cationic, anionic or nonionic surfactant is dissolved and then subjected to reduction treatment. The present invention provides a method for producing a supported noble metal catalyst, which comprises bringing the noble metal hydrosol into contact with a sparingly soluble or insoluble carrier material to cause the noble metal colloid particles contained therein to be supported on the surface of the carrier. be. The noble metal salt used as a raw material in the method of the present invention is a water-soluble chloride, nitrate, etc. of the noble metal. For example, rhodium chloride (), palladium chloride (), chloroplatinic acid, ruthenium chloride (), etc. are preferable. be. In the method of the present invention, it is necessary to use a surfactant as a protective substance for the noble metal hydrosol. Examples of this surfactant include stearyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecylpyridinium chloride, etc. Examples include cationic surfactants, anionic surfactants such as sodium dodecyl sulfate and sodium dodecylbenzenesulfonate, and nonionic surfactants such as polyethylene glycol mono-p-nonyl phenyl ether. In addition, as a reduction treatment method, in addition to alkali metal borohydride salts such as sodium borohydride and potassium borohydride, there are known methods for reducing noble metal salts using water-soluble reducing substances such as hydrazine and formaldehyde. Be taken. To carry out the method of the present invention, predetermined noble metal salts and surfactants are dissolved in water and stirred at 0°C.
The reducing agent or aqueous solution of the reducing agent is added at a temperature of from 100° C. to 100° C., usually at room temperature. A noble metal hydrosol is thus obtained as a highly colored transparent liquid. At this time, the raw material noble metal salt is used so that the concentration in the aqueous solution is in the range of 0.01 to 30 mmol/, and the surfactant is used so that the concentration in the aqueous solution is
It is used in a range of 0.001 to 5%. Further, it is desirable that the reducing agent be used in an amount equal to or more than the same mole relative to the noble metal salt of the raw material. The obtained noble metal hydrosol can be directly used as a homogeneous liquid phase catalyst for an aqueous reaction. In the present invention, a poorly soluble or insoluble substance is further used as a carrier. The supporting treatment is carried out by suspending a substance serving as a carrier in a noble metal hydrosol and stirring the suspension. At this time, as the surface of the carrier becomes colored, the color of the noble metal sol fades, and when it becomes colorless, it can be confirmed that the supporting is completed. If the transition of the noble metal colloid particles from the hydrosol to the carrier is slow, this can be accelerated by appropriately increasing the temperature. The time required for the loading process is in most cases within a few minutes, and in the slowest cases is completed within an hour. In this way, a solid catalyst supporting noble metal colloid particles is obtained. Substances used as carriers include metal hydroxides, oxides, fluorides, carbonates, sulfates, and phosphates that are sparingly soluble or insoluble in water. In addition to alkaline earth metal salts such as magnesium hydroxide, magnesium oxide, magnesium fluoride, magnesium carbonate, calcium hydroxide, calcium fluoride, calcium carbonate, calcium sulfate, calcium phosphate, barium carbonate, and barium sulfate, aluminum hydroxide , titanium oxide, iron oxide (), triiron tetroxide, copper oxide (), copper hydroxide (), zinc oxide, zinc carbonate, zirconium oxide, etc. In addition, ion exchange resins, activated carbon, pulverized coal, activated clay, and the like can also be used as carriers. It is preferable that the material be in the form of a powder finer than 100 mesh, but if the loading rate of the precious metal is low, it is also possible to use other forms, such as granules or molded products. The carrier material is 20 to 10000 times the weight of the noble metal colloid particles to be formed, preferably 50 to 500
Double weight is used. The obtained suspension containing a supported noble metal catalyst can be directly subjected to an aqueous liquid phase reaction, but it is usually allowed to settle by standing or centrifuging, or filtered to disperse the solid catalyst. After cleaning with water or alcohol, dry before use. The first characteristic of the noble metal hydrosol obtained by the process of the invention is that it has a very high catalytic activity. As an example, when compared per unit precious metal when used as an olefin hydrogenation catalyst, the rhodium hydrosol produced by the method of the present invention has:
Shows more than 5 times the activity of commercially available activated carbon-supported rhodium catalysts. The second feature is the high stability of the dispersion state, for example, even after boiling for a long time under normal pressure.
No turbidity or precipitation was observed, and the catalyst remained completely transparent with no reduction in catalytic activity. On the other hand, for example, a noble metal hydrosol using polyvinylpyrrolidone as a protective substance already has a small amount of turbidity immediately after preparation, and the turbidity gradually increases and the catalytic activity decreases due to heat treatment such as boiling. The supported noble metal catalyst obtained by the method of the present invention is also characterized by high catalytic activity. As an example of a supported rhodium catalyst, rhodium hydrosol without a surfactant is The catalytic activity is more than twice that of the supported catalyst obtained from In addition, another feature of the method of the present invention is that by increasing the amount of carrier used in contact with the noble metal hydrosol, a noble metal catalyst with a low supporting ratio can be easily obtained. According to the present invention, a noble metal hydrosol catalyst containing extremely fine noble metal colloidal particles and a solid catalyst supporting noble metal colloidal particles can be easily obtained with good reproducibility. Can be used in a wide range of gas phase catalytic reactions. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Rhodium chloride () (RhCl 3 3H 2 O) 50 μmol
and polyethylene glycol mono-p-nonyl phenyl ether (polymerization degree of polyethylene glycol moiety = 10) 10 mg was dissolved in 95 ml of pure water, and in this,
Sodium borohydride (NaBH 4 ) under stirring
5 ml of a 200 μmol aqueous solution was added dropwise. The pale orange aqueous solution suddenly turned black during the dropwise addition, and the desired rhodium hydrosol was obtained. In a hydrogen atmosphere, 0.4 ml of this rhodium hydrosol (containing 0.2 μg-atom of rhodium) was added to 20 ml of pure water that had been refluxed under argon to remove oxygen. Dilute with a solution containing 2 mg of mono-p-nonylphenyl ether, and add 0.25 mmol of acrylamide while stirring under 1 atm of hydrogen at 30°C.
When 1 ml of an aqueous solution of is dropped, hydrogen absorption begins,
Propionamide was produced. The initial rate of hydrogen absorption is 1.36 mol/sec・g-atomRh
The reaction was completed in about 20 minutes. Example 2 A noble metal hydrosol was prepared in the same manner as in Example 1 by changing the noble metal salt, surfactant, and reducing agent used as raw materials. The initial rate of hydrogenation of acrylamide using the noble metal hydrosol thus obtained in an aqueous solution at 30° C. under 1 atm of hydrogen is shown in the following table.
【表】
実施例 ３
塩化ロジウム（）（RhCl3・3H2O）50μmol
及びヘキサデシルトリメチルアンモニウムヒドロ
キシド10mgを純水95mlに溶解し、これにかくはん
下で、NaBH4200μmolの水溶液５mlを滴下して
黒かつ色で透明なロジウムヒドロゾルを得た。別
途、水酸化マグネシウム0.50ｇを純水50ml中に懸
濁させておき、かくはん下にロジウムヒドロゾル
を注ぎ込み、５分間かくはんした後、静置し、上
澄液を除いた。一夜風乾して大部分の水分を除い
た後、減圧下で乾操し、灰色粉末状の担持型ロジ
ウム触媒を得た。
この担持型ロジウム触媒10mg（ロジウム1μｇ
−atom含有）を50ml容ナス型フラスコに入れ、
内部を水素ガスで置換した後、溶存酸素を除いた
エタノール20mlを加えて30℃、１気圧の水素下で
約１時間かくはんして水素で飽和させた。これに
シクロヘキセン0.25ｍmolを滴下すると水素の吸
収が始まり、シクロヘキサンが生成した。水素吸
収初速度は1.03mol／sec・ｇ−atomRhであり、
反応は約15分で完了した。
実施例 ４
実施例３と同様の操作により、原料となる貴金
属塩、界面活性剤、還元剤及び担体を変えて担持
型貴金属触媒を調製した。こうして得られた担持
型触媒による、エタノール溶液中、30℃、１気圧
の水素下におけるシクロヘキセンの水素化初速度
を次表に示す。[Table] Example 3 Rhodium chloride () (RhCl 3.3H 2 O) 50 μmol
10 mg of hexadecyltrimethylammonium hydroxide were dissolved in 95 ml of pure water, and 5 ml of an aqueous solution of 200 μmol of NaBH 4 was added dropwise thereto under stirring to obtain a black and transparent rhodium hydrosol. Separately, 0.50 g of magnesium hydroxide was suspended in 50 ml of pure water, and rhodium hydrosol was poured into the suspension while stirring. After stirring for 5 minutes, the suspension was allowed to stand, and the supernatant liquid was removed. After air drying overnight to remove most of the moisture, drying was carried out under reduced pressure to obtain a supported rhodium catalyst in the form of a gray powder. 10 mg of this supported rhodium catalyst (1 μg of rhodium
-atom-containing) into a 50ml eggplant-shaped flask,
After purging the inside with hydrogen gas, 20 ml of ethanol from which dissolved oxygen had been removed was added, and the mixture was stirred at 30° C. and under 1 atm of hydrogen for about 1 hour to saturate it with hydrogen. When 0.25 mmol of cyclohexene was added dropwise to this, hydrogen absorption started and cyclohexane was produced. The initial rate of hydrogen absorption is 1.03 mol/sec・g-atomRh,
The reaction was completed in about 15 minutes. Example 4 A supported noble metal catalyst was prepared in the same manner as in Example 3 by changing the raw material noble metal salt, surfactant, reducing agent, and carrier. The initial hydrogenation rate of cyclohexene using the supported catalyst thus obtained in an ethanol solution at 30° C. under 1 atm of hydrogen is shown in the following table.
Claims (1)
中から選ばれた貴金属の塩の水溶液を、陽イオン
性、陰イオン性又は非イオン性の界面活性剤の存
在下に還元処理して貴金属ヒドロゾルを形成させ
ることを特徴とする貴金属触媒の製造方法。 ２ ロジウム、パラジウム、白金、ルテニウムの
中から選ばれた貴金属の塩の水溶液を、陽イオン
性、陰イオン性又は非イオン性の界面活性剤の存
在下に還元処理して貴金属ヒドロゾルを形成さ
せ、次いで、これを難溶性又は不溶性の担体物質
に接触させて、これに含まれる貴金属コロイド粒
子を担体表面上に担持させることを特徴とする貴
金属触媒の製造方法。[Claims] 1. An aqueous solution of a noble metal salt selected from rhodium, palladium, platinum, and ruthenium is reduced in the presence of a cationic, anionic, or nonionic surfactant. A method for producing a noble metal catalyst, which comprises forming a noble metal hydrosol. 2. Reducing an aqueous solution of a salt of a noble metal selected from rhodium, palladium, platinum, and ruthenium in the presence of a cationic, anionic, or nonionic surfactant to form a noble metal hydrosol; A method for producing a noble metal catalyst, which is characterized in that the catalyst is then brought into contact with a poorly soluble or insoluble carrier material, and the noble metal colloid particles contained therein are supported on the surface of the carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57228546A JPS59120249A (en) | 1982-12-27 | 1982-12-27 | Preparation of noble metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57228546A JPS59120249A (en) | 1982-12-27 | 1982-12-27 | Preparation of noble metal catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59120249A JPS59120249A (en) | 1984-07-11 |
| JPS6319217B2 true JPS6319217B2 (en) | 1988-04-21 |
Family
ID=16878076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57228546A Granted JPS59120249A (en) | 1982-12-27 | 1982-12-27 | Preparation of noble metal catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59120249A (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6163780A (en) * | 1984-09-03 | 1986-04-01 | 工業技術院長 | Conductive fiber molded article and its production |
| JPS61107937A (en) * | 1984-11-01 | 1986-05-26 | Agency Of Ind Science & Technol | Preparation of noble metal organosol |
| JPS6468478A (en) * | 1987-09-07 | 1989-03-14 | Agency Ind Science Techn | Metal plating method using silver hydrosol |
| JP3395854B2 (en) * | 1994-02-02 | 2003-04-14 | 日立化成工業株式会社 | Chemical reduction solution of copper oxide and method for producing multilayer printed wiring board using the same |
| JP3609158B2 (en) * | 1995-06-20 | 2005-01-12 | 石原産業株式会社 | Method for supporting inorganic particles |
| JP4505084B2 (en) * | 1999-09-13 | 2010-07-14 | アイノベックス株式会社 | Method for producing metal colloid and metal colloid produced by the method |
| JP3911557B2 (en) * | 2001-12-07 | 2007-05-09 | 独立行政法人産業技術総合研究所 | Method for producing porous material carrying ultrafine metal particles |
| EP1598071A4 (en) | 2003-02-20 | 2006-04-26 | Shetech Co Ltd | Superoxide anion decomposing agent |
| JP4578820B2 (en) * | 2004-02-19 | 2010-11-10 | トヨタ自動車株式会社 | Method for producing gold catalyst and method for using the same |
| CA2635518A1 (en) | 2005-12-27 | 2007-07-05 | Apt Co., Ltd. | Agent for prophylactic and/or therapeutic treatment of chronic obstructive pulmonary disease |
| JP4697213B2 (en) * | 2007-10-29 | 2011-06-08 | 株式会社豊田中央研究所 | Method for decomposing and removing aldehydes |
| JP2009214099A (en) * | 2008-02-14 | 2009-09-24 | Okayama Univ | Method for producing amide compound and catalyst to be used therein |
| KR101204341B1 (en) | 2010-09-30 | 2012-11-23 | 성일하이텍(주) | Methods of Synthesis of ruthenium metal powder using reductants in liquid phase |
| KR20130126541A (en) * | 2012-05-11 | 2013-11-20 | 주식회사 엘지화학 | Hollow metal nano particles |
| US20220218742A1 (en) | 2019-08-20 | 2022-07-14 | Yusei Miyamoto | Agent for reducing malodor of flatulence and/or stool |
-
1982
- 1982-12-27 JP JP57228546A patent/JPS59120249A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59120249A (en) | 1984-07-11 |
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