JP5355084B2 - 担持型金触媒 - Google Patents
担持型金触媒 Download PDFInfo
- Publication number
- JP5355084B2 JP5355084B2 JP2008524420A JP2008524420A JP5355084B2 JP 5355084 B2 JP5355084 B2 JP 5355084B2 JP 2008524420 A JP2008524420 A JP 2008524420A JP 2008524420 A JP2008524420 A JP 2008524420A JP 5355084 B2 JP5355084 B2 JP 5355084B2
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- JP
- Japan
- Prior art keywords
- catalyst
- oxidation
- precursor
- gold
- support
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 77
- 239000010931 gold Substances 0.000 title claims description 57
- 229910052737 gold Inorganic materials 0.000 title claims description 53
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 48
- 239000002243 precursor Substances 0.000 claims description 51
- 239000002253 acid Substances 0.000 claims description 47
- 230000003647 oxidation Effects 0.000 claims description 46
- 238000007254 oxidation reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 150000001720 carbohydrates Chemical class 0.000 claims description 23
- 235000014633 carbohydrates Nutrition 0.000 claims description 23
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 18
- 239000008103 glucose Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
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- 239000008107 starch Substances 0.000 claims description 6
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002774 Maltodextrin Polymers 0.000 claims description 5
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- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 2
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- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
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- 239000004408 titanium dioxide Substances 0.000 claims description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 230000000694 effects Effects 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 11
- 239000000284 extract Substances 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 6
- 208000007976 Ketosis Diseases 0.000 description 6
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- 125000003172 aldehyde group Chemical group 0.000 description 6
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- 150000002482 oligosaccharides Chemical class 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000174 gluconic acid Substances 0.000 description 5
- -1 hydroxide ions Chemical class 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
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- 150000002016 disaccharides Chemical class 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
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Description
担体材料
担体材料として、一例として酸化アルミニウムPuralox KR-90及びNaOをドープした特殊型であるPuralox SCFa-90(いずれもSasol社)を使用した。これらは次のパラメータを有する。
必要量の結晶状テトラクロロ金酸(Chempur社(50%Au))を、最大で使用担体量の気孔容積に相当する容積の溶媒に溶解する。
2. 前駆物質ストック水溶液から希釈した0.2mol/l HClの前駆物質溶液
3. 秤量して水に溶解した前駆物質溶液
4. 前駆物質ストック水溶液から水に希釈した前駆物質溶液
5. 秤量してKOH水溶液に溶解した前駆物質溶液
種々の金含量を有する触媒を得るために、各バッチをそれぞれ異なるクロロ金酸濃度に調合又は希釈した。金属含量0.1ないし5%の金触媒を作ろうとした。バッチごとにそれぞれ2gの金触媒を調製した。
それぞれ別個のバッチで前駆物質溶液を、同時に激しくかき混ぜながら担体材料に徐々に滴下して加えた。気孔容積の飽和とともに担体の吸収能の限界を示す担体材料の湿りが始まることによって、添加の終了が認識される。
含浸した触媒前駆物質を乾燥室で一晩乾燥し(約80℃)、続いて窒素/水素流(約10%H2)で250℃で3時間還元した。次に窒素流中で冷却する。
a)金含量
製造したすべての金触媒でまずICP-AES(高周波誘導結合プラズマ・原子発光分析法)により金含量を決定した。金属含量0.1ないし5%の金触媒が製造された。実験的に決定された金含量を理論的に計算したものと比較した。
金触媒のTEM(透過型電子顕微鏡)写真は、意外なことに1nmないし最大でおよそ10nmの粒度を示す。
すべての触媒についてそれぞれ温度プログラム還元プロフィル(TPRプロフィル)を記録した。図1は触媒のTPRプロフィルを示す。TPRプロフィルから最高温度の明瞭な差が分かる。234℃と最高の還元温度を示すのは、前駆物質を強酸性溶液(この場合2mol/l HCl)に仕込んだ触媒である。前駆物質溶液を水で希釈した触媒は最低を示す。高い還元温度から、担体への金前駆物質の強い吸着を推定することができる。
実施例1で調製された触媒の触媒性能をグルコースのグルコン酸への液相酸化で試験した。
a)選択性
製造した金触媒はこの反応でグルコースのアルデヒド位に対して100%の選択性を示す。
すべての反応で変換は完全であった(100%)。触媒の比較のために最大比活性を取り上げた。
0.3%Au触媒を活性損失なしで20回の“repeated batch(反復バッチ)”テストに使用した。長時間安定性の研究で、触媒はすぐれた長時間安定性を有することが判明した。金の溶出を観察することができなかった。試験回数の増加に伴う活性の増加は、触媒損失による酸素制限の減少が原因と見られるケースである。
助触媒添加物として種々のアルカリ、アルカリ土類及び希土金属を使用し、実施例1により製造した金触媒の活性に対する影響を調べた。
図4は本発明に基づき製造された0.3重量%の金を含む金触媒の最大比活性に対する種々の助触媒の影響を示す。助触媒含量はすべての触媒でそれぞれ0.1重量%である。添加した助触媒はほぼすべて活性増加効果があった。最大の活性増加効果があったのはナトリウム、カリウム、セシウム、カルシウム及び酸化セリウム、さらにはSm2O3であった。
製造
担体材料として鋭錐石含有水化TiO2(Kronos、SBET=288m2/g)を使用した。70℃に熱し、0.2NのNaOHでpH値6.5に整えた蒸留水1リットル中50gの TiO2懸濁水に、水250ml中のテトラクロロ金酸(HAuCl4×3H2O)500mgを一定のpH値で激しく攪拌しながら3時間以内に滴下して加えた。バッチを70℃でさらに1時間攪拌した。室温に冷却した後、あらかじめ0.2NのNaOHでpH値を6.5に整えたクエン酸マグネシウム溶液(水50mlに2,318g MgHC6H5O7×5H2O)を加える。1時間の攪拌時間の後に固体を遠心分離し、水で3回洗浄し、続いて真空乾燥室で<50hPaの圧力で室温で17時間、そして50℃で4時間乾燥する。得た前駆物質を軽く摩砕し、空気中で1K/minの温度上昇率で250℃に加熱し、この温度で3時間活性化する。
TEM(透過型電子顕微鏡):粒径5nm以下の粒子が優勢であり、まれに粒径約20nmの粒子がある。
グルコース酸化
0. 5%Auを含むTiO2担体触媒(0.5%Au/TiO2)149型(ACA)をグルコース
酸化に使用した。次の反応条件でグルコース酸化を行った。反応容積(バッチ):500ml、触媒量:1g/l、基質初期濃度:100mmol/l、pH値:9、温度:40℃、圧力:1bar、O2ガス補給率:500ml/min、攪拌速度:700rpm。
グルコース変換率 100%
最大比活性 416mmol グルコース・gmetal −1・min−1
グルコン酸に対する選択性 >99.5%
Claims (19)
- a)乾燥した形の担体を調製し、
b)担体とクロロ金酸前駆物質の水溶液を接触させ、その際含浸した触媒前駆物質が得られるように、溶液の容積は最大で担体の気孔容積に相当し、
c)含浸した触媒前駆物質を乾燥する
の諸段階を含む、多孔質金属酸化物担体とクロロ金酸前駆物質からアルコール、アルデヒド、ポリヒドロキシ化合物、及び炭水化物から選ばれた有機化合物の酸化のための担持型金触媒を製造する方法において、クロロ金酸前駆物質の水溶液中でテトラクロロ錯体[AuCl4]−が優勢である方法。 - 段階b)でクロロ金酸前駆物質の水溶液を、担体が溶液のそれ以上の容積を吸収できなくなるまでの間だけ、乾燥した担体に徐々に加える請求項1に記載の方法。
- クロロ金酸前駆物質の水溶液が、酸濃度が0.1mol/lないし12mol/lの、HAuCl4の酸水溶液である請求項1又は2に記載の方法。
- 別の段階d)で触媒前駆物質の還元を水素流中で250℃以上の温度で行う請求項1ないし3のいずれか1つに記載の方法。
- 段階d)で還元を10分ないし300分間行う請求項4に記載の方法。
- 段階d)で水素流が5容積%ないし15容積%の水素含量と場合によっては不活性ガスを含む請求項4又は5に記載の方法。
- 別の段階d)で触媒前駆物質の還元を液相還元として行う請求項1ないし3のいずれか1つに記載の方法。
- 段階c)で乾燥が60℃ないし200℃の温度で行われる請求項1ないし7のいずれか1つに記載の方法。
- 金属酸化物担体が酸化アルミニウム、酸化ケイ素及び二酸化チタンから選ばれる請求項1ないし8のいずれか1つに記載の方法。
- 担体及び/又は前駆物質の溶液にさらにアルカリ金属、アルカリ土類金属及び希土金属の酸化物から選ばれたドーピング添加物を加える請求項1ないし9のいずれか1つに記載の方法。
- アルコール、アルデヒド、ポリヒドロキシ化合物、及び炭水化物から選ばれた有機化合物の酸化に用いる金属酸化物担持型金触媒を製造するための、テトラクロロ錯体[AuCl4]−が優勢なHAuCl4溶液又は懸濁液のクロロ金酸前駆物質の使用。
- 請求項1ないし10のいずれか1つに記載の方法により製造することができる、アルコール、アルデヒド、ポリヒドロキシ化合物、及び炭水化物から選ばれた有機化合物の酸化のための金属酸化物担持型金触媒。
- 酸化が選択酸化である、請求項12に記載の触媒。
- 担体上の金粒子の平均粒度が10nm未満であることを特徴とする請求項12又は13に記載の触媒。
- 金の割合が0.01重量%ないし10重量%であることを特徴とする請求項12ないし14のいずれか1つに記載の触媒。
- アルコール、アルデヒド、ポリヒドロキシ化合物、及び炭水化物から選ばれた有機化合物の酸化のための請求項12ないし15のいずれか1つに記載の触媒の使用。
- グルコース、ガラクトース、マンノース、キシロース及びリボース;マルトース、ラクトース、セロビオース及びイソマルトース;パラチノース;デンプンシロップ;マルトデキストリン並びにこれらの混合物から選ばれた炭水化物の酸化のための請求項16に記載の使用。
- 酸化が選択酸化である、請求項17に記載の使用。
- アルドン酸の製造のための請求項12ないし15のいずれか1つに記載の触媒の使用。
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DE102005036890A DE102005036890A1 (de) | 2005-08-05 | 2005-08-05 | Geträgerter Goldkatalysator |
DE102005036890.5 | 2005-08-05 | ||
PCT/EP2006/007584 WO2007017157A1 (de) | 2005-08-05 | 2006-08-01 | Geträgerter goldkatalysator |
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WO2008148549A2 (en) * | 2007-06-05 | 2008-12-11 | Dsm Ip Assets B.V. | Novel reaction with a gold catalyst |
DE102008053607A1 (de) * | 2008-10-20 | 2010-04-22 | Südzucker AG Mannheim/Ochsenfurt | Solubilisierungsmittel für Metallionen |
JP5588657B2 (ja) * | 2009-11-10 | 2014-09-10 | 旭化成ケミカルズ株式会社 | カルボン酸の製造方法 |
CN103097296B (zh) | 2010-09-16 | 2015-02-18 | 旭化成化学株式会社 | 二氧化硅系材料及其制造方法以及贵金属负载物和使用其作为催化剂的羧酸类的制造方法 |
KR101065242B1 (ko) * | 2010-12-14 | 2011-09-19 | 한국과학기술연구원 | 선택적 탈질 환원 촉매 및 이산화 티타늄 수화물 슬러리를 이용한 그 제조방법 |
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RU2603195C1 (ru) * | 2015-11-13 | 2016-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Юго-Западный государственный университет" (ЮЗГУ) | Способ получения лактобионовой кислоты |
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IL108635A (en) * | 1993-02-18 | 1997-09-30 | Grigorova Bojidara | Catalyst for use in an oxidation reaction |
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US6821923B1 (en) * | 1999-04-08 | 2004-11-23 | Dow Global Technologies Inc. | Method of preparing a catalyst containing gold and titanium |
DE10205873A1 (de) | 2002-02-13 | 2003-08-21 | Zsw | Metalloxidgeträgerte Au-Katalysatoren, Verfahren zu deren Herstellung sowie deren Verwendung |
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WO2005003072A1 (en) | 2003-07-01 | 2005-01-13 | Universita' Degli Studi Di Milano | Process and catalyst for the preparation of aldonic acids |
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DE102005036890A1 (de) | 2007-02-08 |
CA2618241C (en) | 2011-12-20 |
US8329613B2 (en) | 2012-12-11 |
BRPI0614134B1 (pt) | 2015-12-15 |
WO2007017157A1 (de) | 2007-02-15 |
CN101237931A (zh) | 2008-08-06 |
ZA200800967B (en) | 2009-07-29 |
KR101201208B1 (ko) | 2012-11-15 |
IL188998A (en) | 2014-03-31 |
RU2378048C2 (ru) | 2010-01-10 |
BRPI0614134B8 (pt) | 2017-02-21 |
RU2008108518A (ru) | 2009-09-10 |
BRPI0614134C8 (pt) | 2017-04-11 |
CA2618241A1 (en) | 2007-02-15 |
KR20080035636A (ko) | 2008-04-23 |
ES2654839T3 (es) | 2018-02-15 |
WO2007017157A8 (de) | 2007-06-14 |
JP2009502491A (ja) | 2009-01-29 |
BRPI0614134A2 (pt) | 2011-03-09 |
CN101237931B (zh) | 2011-07-27 |
EP1912739A1 (de) | 2008-04-23 |
IL188998A0 (en) | 2008-08-07 |
US20090221849A1 (en) | 2009-09-03 |
EP1912739B1 (de) | 2017-10-11 |
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