ES2654839T3 - Catalizador de oro soportado - Google Patents
Catalizador de oro soportado Download PDFInfo
- Publication number
- ES2654839T3 ES2654839T3 ES06762915.4T ES06762915T ES2654839T3 ES 2654839 T3 ES2654839 T3 ES 2654839T3 ES 06762915 T ES06762915 T ES 06762915T ES 2654839 T3 ES2654839 T3 ES 2654839T3
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- ES
- Spain
- Prior art keywords
- support
- solution
- precursor
- acid
- gold
- 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.)
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000010931 gold Substances 0.000 title abstract description 13
- 229910052737 gold Inorganic materials 0.000 title abstract description 13
- 239000003054 catalyst Substances 0.000 title abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 7
- 239000012018 catalyst precursor Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- JGSSBWAWLXYSMC-UHFFFAOYSA-N 1-chloro-7,9-dihydro-3h-purine-2,6,8-trione Chemical compound O=C1N(Cl)C(=O)NC2=C1NC(=O)N2 JGSSBWAWLXYSMC-UHFFFAOYSA-N 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 229910004042 HAuCl4 Inorganic materials 0.000 abstract 1
- 150000001720 carbohydrates Chemical class 0.000 abstract 1
- 235000014633 carbohydrates Nutrition 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 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 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
-
- 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
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
Procedimiento para la preparación de un catalizador de oro soportado para la oxidación de hidratos de carbono a partir de soporte de óxido de metal poroso y precursor de ácido cloroáurico, que contiene las etapas: a) facilitar el soporte en forma seca, b) llevar a contacto el soporte con una solución del precursor de ácido cloroáurico, en el que el volumen de la solución es como máximo tan grande como el volumen de poros del soporte, de modo que se obtiene precursor de catalizador impregnado, y c) secar el precursor de catalizador impregnado, en el que la solución del precursor de ácido cloroáurico es una solución de HAuCl4 en ácido clorhídrico acuoso con una concentración de 0,1 mol/l a 12 mol/l de ácido.
Description
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Impregnación de los soportes de óxido de metal, procedimiento de humedad incipiente
Las soluciones de precursor se añadieron gota a gota en mezclas de reacción en cada caso separadas con al mismo tiempo mezclado intensivo paulatinamente al material de soporte. El final de la adición puede distinguirse mediante humedad incipiente del material de soporte, que indica la saturación del volumen de poros y con ello el límite de la capacidad de absorción del soporte.
Secado, reducción
Los precursores de catalizador impregnados se secaron durante la noche en el armario de secado (aprox. 80 ºC) y a continuación se redujeron durante 3 h a 250 ºC en el flujo de nitrógeno/hidrógeno (aprox. 10 % de H2). Después de esto se enfría en el flujo de nitrógeno.
Resultados
a) Contenido en oro
En todos los catalizadores de oro preparados se determinó en primer lugar el contenido en oro por medio de ICP-AES. Se prepararon catalizadores de oro con contenidos en metal entre el 0,1 % y el 5 %. Los contenidos en oro determinados de manera experimental se comparan con los calculados teóricamente.
Los contenidos en oro teóricos y contenidos en oro reales se correlacionan en todas las mezclas de reacción de manera excelente. Se logra aplicar el oro sin pérdidas sobre el soporte.
b) Tamaño de partícula
Los registros TEM de los catalizadores de oro muestran sorprendentemente tamaños de partícula de 1 a como máximo aproximadamente 10 nm.
c) Temperatura de reducción
De todos los catalizadores se registraron en cada caso perfiles de la reducción a temperatura programada (perfiles TPR). La figura 1 muestra los perfiles TPR de los catalizadores. A partir de los perfiles TPR pueden distinguirse claras diferencias en las temperaturas del máximo. La temperatura de reducción más alta la muestra con 234 ºC el catalizador en el que el precursor se pesó en solución fuertemente ácida (en este caso: 2 mol/l de HCl); la más baja la muestra el catalizador en el que la solución de precursor se diluyó con agua. De una temperatura de reducción alta puede deducirse una fuerte adsorción del precursor de oro en el soporte.
Ejemplo 2: oxidación catalítica de glucosa
El rendimiento catalítico de los catalizadores preparados según el ejemplo 1 se sometió a ensayo en la oxidación de fase líquida de glucosa para dar ácido glucónico.
La reacción se realizó en un reactor de vidrio calentado (volumen 500 ml) a 40 ºC. La gasificación se realizó mediante una frita de vidrio con una velocidad de flujo de oxígeno de 500 ml/min. La concentración inicial de glucosa ascendía a 100 mmol/l. El valor de pH se mantuvo constante a pH 9 con ayuda de un aparato de titulación (Titroline alpha, empresa Schott) y 2 mol/l de solución de hidróxido de sodio. Dado que en el caso de ácido glucónico se trata de un ácido monocarboxílico, puede deducirse con un 100 % de selectividad del volumen de solución de hidróxido consumido directamente la cantidad de ácido producida. Adicionalmente se realizó un control por medio de HPLC.
Resultados
a) Selectividad
Los catalizadores de oro preparados muestran en esta reacción el 100 % de selectividad para la posición de aldehído de la glucosa.
Como comparación sirvió Puralox SCFa-90 (“no impurificado” en la figura 4) y el Puralox SCFa-90 impurificado con NaO (“impurificado con Sasol” en la figura 4).
b) Actividad catalítica
La conversión era completa en todas las reacciones (100 %). Para la comparación de los catalizadores se consultó la actividad máxima, específica.
7
Claims (1)
-
imagen1
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005036890A DE102005036890A1 (de) | 2005-08-05 | 2005-08-05 | Geträgerter Goldkatalysator |
| DE102005036890 | 2005-08-05 | ||
| PCT/EP2006/007584 WO2007017157A1 (de) | 2005-08-05 | 2006-08-01 | Geträgerter goldkatalysator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2654839T3 true ES2654839T3 (es) | 2018-02-15 |
Family
ID=37530634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES06762915.4T Active ES2654839T3 (es) | 2005-08-05 | 2006-08-01 | Catalizador de oro soportado |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US8329613B2 (es) |
| EP (1) | EP1912739B1 (es) |
| JP (1) | JP5355084B2 (es) |
| KR (1) | KR101201208B1 (es) |
| CN (1) | CN101237931B (es) |
| BR (1) | BRPI0614134C8 (es) |
| CA (1) | CA2618241C (es) |
| DE (1) | DE102005036890A1 (es) |
| ES (1) | ES2654839T3 (es) |
| IL (1) | IL188998A (es) |
| RU (1) | RU2378048C2 (es) |
| WO (1) | WO2007017157A1 (es) |
| ZA (1) | ZA200800967B (es) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| RU2468861C1 (ru) * | 2011-05-04 | 2012-12-10 | Государственное образовательное учреждение высшего профессионального образования "Юго-Западный государственный университет" (ЮЗГУ) | Способ получения катализатора на пористом металлооксидном носителе для окисления углеводов |
| RU2603195C1 (ru) * | 2015-11-13 | 2016-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Юго-Западный государственный университет" (ЮЗГУ) | Способ получения лактобионовой кислоты |
| RU2613681C1 (ru) * | 2016-02-24 | 2017-03-21 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кемеровский государственный университет" (КемГУ) | Способ получения золото-углеродного наноструктурированного композита |
| EP3544947B1 (en) * | 2016-11-24 | 2023-09-13 | Topsoe A/S | A method for producing glycolic acid and/or glycolate |
| RU2663905C1 (ru) * | 2018-03-30 | 2018-08-13 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) | Катализатор, способ его приготовления и способ получения n-(фосфонометил)-глицина |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63252908A (ja) * | 1987-04-08 | 1988-10-20 | Agency Of Ind Science & Technol | 金超微粒子固定化酸化物、その製造法、酸化触媒、還元触媒、可燃性ガスセンサ素子、及び電極用触媒 |
| IL108635A (en) * | 1993-02-18 | 1997-09-30 | Grigorova Bojidara | Catalyst for use in an oxidation reaction |
| JP3813646B2 (ja) * | 1995-06-29 | 2006-08-23 | 株式会社コスモ総合研究所 | 水蒸気改質触媒の製造方法および水素製造方法 |
| DE19734974A1 (de) | 1997-08-13 | 1999-02-25 | Hoechst Ag | Verfahren zur Herstellung von porös geträgerten Metall-Nanopartikel-haltigen Katalysatoren, insbesondere für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat |
| 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 |
| DE10362249B4 (de) * | 2003-05-05 | 2014-05-15 | Südzucker AG Mannheim/Ochsenfurt | C1-selektive Oxidation von Oligosacchariden und die Verwendung eines Kohlenstoff geträgerten Gold-Katalysators für diese Oxidation |
| WO2005003072A1 (en) | 2003-07-01 | 2005-01-13 | Universita' Degli Studi Di Milano | Process and catalyst for the preparation of aldonic acids |
| JP2005154302A (ja) | 2003-11-21 | 2005-06-16 | Mitsubishi Gas Chem Co Inc | 糖質の酸化方法 |
| GB2408956A (en) * | 2003-12-11 | 2005-06-15 | Johnson Matthey Plc | Reforming catalyst |
-
2005
- 2005-08-05 DE DE102005036890A patent/DE102005036890A1/de not_active Withdrawn
-
2006
- 2006-08-01 BR BRPI0614134A patent/BRPI0614134C8/pt active IP Right Grant
- 2006-08-01 CN CN2006800290629A patent/CN101237931B/zh active Active
- 2006-08-01 RU RU2008108518/04A patent/RU2378048C2/ru active
- 2006-08-01 ZA ZA200800967A patent/ZA200800967B/xx unknown
- 2006-08-01 KR KR1020087003763A patent/KR101201208B1/ko active IP Right Grant
- 2006-08-01 WO PCT/EP2006/007584 patent/WO2007017157A1/de active Search and Examination
- 2006-08-01 ES ES06762915.4T patent/ES2654839T3/es active Active
- 2006-08-01 JP JP2008524420A patent/JP5355084B2/ja active Active
- 2006-08-01 EP EP06762915.4A patent/EP1912739B1/de active Active
- 2006-08-01 US US11/997,594 patent/US8329613B2/en active Active
- 2006-08-01 CA CA2618241A patent/CA2618241C/en active Active
-
2008
- 2008-01-24 IL IL188998A patent/IL188998A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005036890A1 (de) | 2007-02-08 |
| CA2618241C (en) | 2011-12-20 |
| US8329613B2 (en) | 2012-12-11 |
| JP5355084B2 (ja) | 2013-11-27 |
| 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 |
| 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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