EP2117703A1 - Kohlenstoff-geträgerter goldkatalysator, verfahren zu seiner herstellung und verwendung zur oxidation von organischen verbindungen - Google Patents

Kohlenstoff-geträgerter goldkatalysator, verfahren zu seiner herstellung und verwendung zur oxidation von organischen verbindungen

Info

Publication number
EP2117703A1
EP2117703A1 EP08707394A EP08707394A EP2117703A1 EP 2117703 A1 EP2117703 A1 EP 2117703A1 EP 08707394 A EP08707394 A EP 08707394A EP 08707394 A EP08707394 A EP 08707394A EP 2117703 A1 EP2117703 A1 EP 2117703A1
Authority
EP
European Patent Office
Prior art keywords
precursor
catalyst
carbon
solution
oxidation
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.)
Withdrawn
Application number
EP08707394A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alireza Haji Begli
Christine KRÖNER
Nadine Decker
Ulf PRÜSSE
Klaus-Dieter Vorlop
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suedzucker AG
Original Assignee
Suedzucker AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suedzucker AG filed Critical Suedzucker AG
Publication of EP2117703A1 publication Critical patent/EP2117703A1/de
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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

Definitions

  • the invention relates to processes for the preparation of supported gold catalysts with porous carbon support and chloroauric acid precursor.
  • the invention also relates to carbon-supported
  • Gold catalysts and their use for the oxidation of, in particular, alcohols, aldehydes, polyhydroxy compounds and carbohydrates are particularly useful.
  • reaction by-products can often no longer or only with difficulty be separated from the product mixture.
  • the purity of a product is linked to its cleanability.
  • Many reaction products are regarded as highly pure only because contained reaction by-products are no longer separable. In some cases, the reaction by-products, as such, are not detectable or differentiable by common methods.
  • Dioxygen as an oxidizing agent allow and in addition to high activity and selectivity also have a long life.
  • Supported gold catalysts are known. They are mainly used for the oxidation of CO or propene in the gas phase and for selective hydrogenation. Carbon-supported gold catalysts can also be used for the selective oxidation of D-glucose to D-gluconic acid in the liquid phase.
  • DE 103 199 17 A1 discloses supported gold catalysts with nanodisperse-distributed gold particles on carbon or metal oxide supports. These are mainly used for the C1-selective oxidation of glucose and other carbohydrates. However, the activity of these catalysts is not satisfactory.
  • the technical problem underlying the present invention is to provide improved supported gold catalysts and processes for their preparation which have improved activity and selectivity, especially in the oxidation of organic compounds such as alcohols, aldehydes and polyhydroxy compounds.
  • the invention has the technical problem of providing methods for the selective and effective oxidation of carbohydrates, in particular for the production of aldonic acids, which overcome the disadvantages of the prior art.
  • step a) the carbon support is provided, in a step b ) the carrier is brought into contact with an aqueous solution or suspension of the chloroauric acid precursor.
  • step b) an impregnated catalyst precursor is obtained therefrom, which is dried in a subsequent step c).
  • inventive method is particularly characterized in that in step a) of
  • Carrier in dry and preferably powdered or granulated form or as a shaped body is provided and that in step b) the volume of the aqueous solution or suspension of the chloroauric acid precursor is maximally selected so large that it corresponds to the pore volume of the carrier. It can be chosen smaller, but not bigger than that
  • the volume of the aqueous precursor solution supplied to the dry carrier is preferably determined empirically by adding the precursor solution stepwise to the dry carrier until the carrier can no longer absorb any further volume of the precursor solution. This can be recognized above all by the onset of moist appearance of the carrier material.
  • a specific absorption capacity [in ml / g of catalyst support] results for each carbon carrier variety, which depends above all on the surface / volume ratio, the pore size and the degree of drying of the carbon carrier.
  • dry is meant that the porous carbon support contains substantially no moisture in the pore volume, so that precursor solution can be included in the pore volume.
  • steps a) to c) are carried out two or more times in succession.
  • steps b) and c) are carried out simultaneously, that is, parallel to each other in a reaction mixture.
  • the contacting of the carbon support with the chloroauric acid precursor takes place in step b)
  • the precursor Dropwise addition of the precursor to the carrier with stirring.
  • the precursor is sprayed onto the carrier, wherein the carrier is preferably stirred.
  • the carrier is dried with the applied precursor (step c)).
  • the contacting of the precursor with the carrier takes place in a coating pan or a pelletizing plate, with preferably being dropped or sprayed on and optionally dried at the same time.
  • the carrier is in a fluidized bed and the precursor is introduced into the fluidized bed, preferably sprayed; In this case, the support is preferably dried with the applied precursor (step c)).
  • chloroauric acid precursor preference is given to an acidic solution or
  • tetrachloroauric acid HAV 4
  • hydrochloric acid tetrachloroauric acid
  • the pH is the finished
  • Precursor solution always 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, and most preferably always 1 or less.
  • the precursor solution used according to the invention contains at least one further acid.
  • Acid and hydrochloric acid more inorganic or organic acids are used.
  • the required amount of tetrachloroauric acid is particularly preferably weighed and dissolved directly into the aqueous acid.
  • the required amount of tetrachloroauric acid is particularly preferably weighed and dissolved directly into the aqueous acid.
  • Tetrachloroauric acid aqueous hydrochloric acid is preferably used in a concentration of 0.1 mol / l to 12 mol / l, 1 mol / l to 4 mol / l and particularly preferably 2 mol / l.
  • the catalysts prepared according to the invention surprisingly have very small and active particle sizes of less than 10 nm, in particular from 1 nm to 10 nm, preferably from 1 nm to 9 nm, especially from 1 nm to 5 nm or even from 1 nm to 2 nm.
  • the inventors have succeeded in preparing catalytically active gold particles in quantities of well below 10 nm on a carbon support by the "incipient wetness" method
  • the obtained gold catalysts show a hitherto unattained activity and selectivity, for example in the conversion of glucose or lactose, in particular by using a strongly acidic precursor solution (for example 2 mol / l HCl as solvent for tetrachloroauric acid) and when using succeeded the preparation of the so far a catalyst prepared erfmdungshack Neillbei the glucose oxidation active carbon-supported gold catalyst. an activity of about 2000 mmol gMetaii 1 min "-1.
  • HAuCI 4 is not stable in aqueous solution but is hydrolyzed. A successive exchange of the chloride for water and hydroxy groups takes place in several equilibria connected in series: [AuCl 4 ] " , [AuCl 3 (OH)] -, [AuCl 2 (OH) 2 ] -, [AuCl 2 (OH)] , [AuCl (OH) 2 ],
  • the hydrolysis can be prevented or influenced.
  • step c) at temperatures of greater than or equal to room temperature, preferably from 60 0 C to 200 0 C, more preferably dried from 60 0 C to 100 0 C.
  • the catalyst precursor is reduced.
  • the hydrogen stream has a hydrogen content of 5% by volume to 15% by volume, preferably 10% by volume.
  • the hydrogen stream may optionally contain at least one inert gas, such as nitrogen or noble gas. Particularly preferred is the
  • Hydrogen stream of hydrogen gas and at least one inert gas can be carried out as a liquid phase reduction in a conventional manner with suitable reducing agents such as sodium borohydride, formate salts, carbohydrates, formaldehyde or hydrazine.
  • suitable reducing agents such as sodium borohydride, formate salts, carbohydrates, formaldehyde or hydrazine.
  • the reduction in step d) is preferably carried out at temperatures of greater than or equal to 250 ° C. According to the invention, the reduction preferably takes place from 10 minutes to 300 minutes, preferably from 80 to 120 minutes.
  • At least one doping additive is added to the carrier and / or the aqueous solution or suspension of the chloroauric acid precursor.
  • This is preferred selected from oxides of the alkali metals, the alkaline earth metals and the rare earth metals. Particular preference is given to doping with sodium, potassium, cesium, calcium, cerium and / or samarium.
  • the at least one doping additive is added in a proportion of 0.01% by weight to 1% by weight.
  • a further subject of the present invention is therefore also the use of a chloroauric acid precursor which contains or consists of a solution or suspension of tetrachloroauric acid (HAuCl 4 ) in a solvent, the solvent being aqueous acid in a concentration of 0.1 mol / l to 12 mol / l, preferably from 1 mol / l to 4 mol / l, particularly preferably from 2 mol / l, is.
  • the acid is hydrochloric acid (HCl).
  • the hydrochloric acid is preferably present in conjunction with at least one further acid.
  • this chloroauric acid precursor is preferably used for producing the carbon-supported gold catalyst according to one of the methods described above.
  • Another object of the present invention is also a carbon-supported gold catalyst, which is produced or prepared by the aforementioned method.
  • the catalyst according to the invention is particularly characterized in that the mean size of the gold particles on the support is substantially less than 10 nm, preferably 5 nm or less, particularly preferably from 1 nm to 2 nm.
  • the catalyst according to the invention preferably has a gold content of from 0.01% by weight to 10% by weight, preferably from 0.01% by weight to 2% by weight, particularly preferably of 0.3% by weight.
  • a further object of the present invention is the use of the aforementioned inventive catalyst for the oxidation of organic starting materials, which are selected in particular from alcohols, aldehydes and polyhydroxy compounds. According to the invention, the catalyst is preferably used in a heterogeneous catalysis.
  • the catalyst is present as a solid, while the starting materials to be oxidized in fluid phase, for example as an aqueous solution, are present.
  • the dioxygen used preferably for the oxidation is then bubbled through as a gas through the liquid phase and distributed and dissolved by intensive stirring in the liquid phase.
  • the catalyst is preferably used in the form of a powder or granules.
  • moldings for example cylinders, hollow cylinders, spheres or strands are used.
  • an aqueous solution or suspension of the educt or educt mixture to be oxidized is prepared which contains at least about 10 mmol / l, preferably at least about 100 mmol / l, 150 mmol / l, 200 mmol / l, 250 mmol / l, 1000 mmol / l or 1500 mmol / l. Subsequently, the aqueous educt
  • Solution of preferably powdered catalyst according to the invention in an amount of about 10 mg / l to 10 g / l added, preferably per liter of about 1 g of catalyst are used.
  • the ratio between the amount of starting material (s) to be oxidized and the amount of gold contained on the carbon support is at least about 300-400,000, preferably at least 300, 500, 1,000, 2,000, 4,000, 10,000, 20,000, 50,000, 100,000 , 200,000 or 400,000.
  • the oxidation of the educt or starting material mixture is preferably carried out at a pH of from 7 to 11, preferably from 8 to 10.
  • the pressure is preferably about 1 bar to about 25 bar.
  • the gold catalysts according to the invention are therefore also suitable for the selective oxidation of carbohydrates. This is understood in particular to mean the oxidation of an oxidizable aldehyde group on the C1 carbon of a carbohydrate to a carboxyl group, whereas alcohol groups on other carbon atoms of the carbohydrate are not oxidized. As a result, therefore, aldonic acid is preferably obtained.
  • the carbohydrates preferably used according to the invention are preferably aldoses which have an oxidizable aldehyde group on the C 1 carbon, or 2-ketoses in which an oxidisable aldehyde group can be introduced at the C 1 -carbon atom.
  • the selective oxidation of the aldehyde group of an aldose gives an aldonic acid. In the selective oxidation of a mixture of aldoses, therefore, a mixture of different aldonic acids is obtained.
  • the present invention therefore also relates to the use of the catalysts of the invention for preparing an aldonic acid or a mixture of various aldonic acids by selective oxidation of one or more aldoses with an oxidisable aldehyde group.
  • the present invention therefore also relates to the use for producing an aldonic acid or a mixture of different aldonic acids using one or more 2-ketoses, wherein the 2-ketose (s) first in the tautomeric (al) form (s) with an oxidizable Aldehyde group transferred and then using the
  • Catalyst is selectively oxidized / become.
  • the carbohydrates to be oxidized comprise both monomeric polyhydroxy aldehydes or polyhydroxy ketones, ie monosaccharides, their dimers to decamers, that is to say oligosaccharides such as disaccharides, trisaccharides, etc., and the macromolecular ones
  • polysaccharides are understood to mean compounds of the general chemical formula C n H 2n O n having 3 to 7 oxygen functions, where natural monosaccharides are essentially hexoses and pentoses
  • oligosaccharides is meant compounds which are obtained by combining 2 to 10 monosaccharide molecules with elimination of water.
  • the catalyst for the selective oxidation of carbohydrates selected from monosaccharides such as glucose,
  • Ketoses such as palatinose and starch syrups and maltodextrins as well
  • the carbohydrate to be oxidized is an oligosaccharide, in particular a disaccharide.
  • the disaccharide to be oxidized is preferably a disaccharide aldose such as maltose, lactose, cellobiose or isomaltose.
  • maltobionic acid is obtained as the oxidation product.
  • by-product-free lactobionic acid is obtained as the oxidation product in the lactose oxidation.
  • the oligosaccharide to be oxidized is a disaccharide ketose.
  • the disaccharide ketose to be oxidized is preferably palatinose (isomaltulose). According to the invention, prior to the oxidation, palatinose is converted into the tautomeric aldose form, which is then oxidized.
  • the carbohydrate to be oxidized is a maltodextrin.
  • Maltodextrins are water soluble carbohydrates obtained by enzymatic starch degradation, especially dextrose equivalents, having a chain length of 2 to 30, preferably 5 to 20 anhydroglucose units and a proportion of
  • Maltose In the selective oxidation of maltodextrin using the method of the invention is an oxidation product obtained according to the invention according to the composition in addition to the oligosaccharide-aldonic acids having a proportion of maltobionic acid and gluconic acid.
  • the carbohydrate to be oxidized is a starch syrup. Under a corn syrup becomes one
  • Glucose syrup understood, which is obtained from starch and is present above all as a purified aqueous solution, wherein the dry matter is usually at least 70%.
  • the carbohydrate to be oxidized is a furfural.
  • the furfural to be oxidized is preferred
  • HMF Hydroxymethylfurfural
  • GMF glycosyloxymethylfurfural
  • the required amount of tetrachloroauric acid in crystalline form (from Chempur (50% Au)) is dissolved in the volume of a solvent that corresponds at most to the pore volume of the amount of carrier used.
  • each batch was prepared or diluted several times in different concentrations. Gold catalysts with metal contents between 0.1 and 5% should be produced. In each case 2 g of gold catalyst was prepared per batch.
  • the precursor solutions were added dropwise in separate batches with simultaneous intensive mixing gradually to the support material.
  • the end of the addition can be recognized by onset of moisture of the carrier material, which indicates the saturation of the pore volume and thus the limit of the absorption capacity of the carrier. Drying, reduction
  • the impregnated catalyst precursors were dried overnight in a drying oven (about 80 ° C.) and then reduced for 3 hours at 250 ° C. in a nitrogen / hydrogen stream (about 10% H 2 ). It is then cooled in a stream of nitrogen.
  • the gold content was first determined by ICP-AES. Gold catalysts were produced with metal contents between 0.1 and 5%. The experimentally determined gold grades are compared with the theoretically calculated ones. The theoretical gold grades and actual gold grades correlate excellently in all approaches. It succeeds to apply the gold lossless on the carrier.
  • the TEM analysis of the gold catalysts show particle sizes from 1 to a maximum of approximately 10 nm.
  • Reduction temperature shows the catalyst in which the precursor was weighed in strongly acidic solution: 2 mol / l HCl; the lowest shows the catalyst in which the precursor solution was diluted with water. From a high reduction temperature can be concluded on a strong adsorption of the Goldprecursors to the carrier.
  • the catalytic performance of the catalysts prepared according to Example 1 was in the liquid phase oxidation of glucose to
  • Gluconic acid tested The reaction was (500 ml volume) is carried out in a temperature-controlled glass reactor at 40 0 C. The fumigation was carried out by a glass frit with an oxygen flow rate of 500 ml / min. The initial glucose concentration was 100 mmol / l. The pH was kept constant at pH 9 using a titrator (Titroline alpha, Schott.) And 2 mol / l potassium hydroxide solution. Since gluconic acid is a monocarboxylic acid, at 100% selectivity from the volume of liquor consumed, it is possible to directly deduce the amount of acid produced. In addition, a check was carried out by means of HPLC.
  • the gold catalysts prepared show 100% selectivity for the aldehyde position (C1) of the glucose in this reaction.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP08707394A 2007-02-03 2008-01-30 Kohlenstoff-geträgerter goldkatalysator, verfahren zu seiner herstellung und verwendung zur oxidation von organischen verbindungen Withdrawn EP2117703A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007005528A DE102007005528A1 (de) 2007-02-03 2007-02-03 Kohlenstoff-geträgerter Goldkatalysator
PCT/EP2008/000694 WO2008095629A1 (de) 2007-02-03 2008-01-30 Kohlenstoff-geträgerter goldkatalysator, verfahren zu seiner herstellung und verwendung zur oxidation von organischen verbindungen

Publications (1)

Publication Number Publication Date
EP2117703A1 true EP2117703A1 (de) 2009-11-18

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EP08707394A Withdrawn EP2117703A1 (de) 2007-02-03 2008-01-30 Kohlenstoff-geträgerter goldkatalysator, verfahren zu seiner herstellung und verwendung zur oxidation von organischen verbindungen

Country Status (11)

Country Link
US (1) US20100137637A1 (ru)
EP (1) EP2117703A1 (ru)
JP (1) JP2010517740A (ru)
KR (1) KR20090108087A (ru)
CN (1) CN101631610A (ru)
BR (1) BRPI0807009A2 (ru)
DE (1) DE102007005528A1 (ru)
EA (1) EA200901033A1 (ru)
IL (1) IL200101A0 (ru)
WO (1) WO2008095629A1 (ru)
ZA (1) ZA200905368B (ru)

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JP5290599B2 (ja) * 2008-03-17 2013-09-18 公立大学法人首都大学東京 金微粒子を担体に分散・固定化する方法
CN101591233B (zh) * 2009-06-19 2012-06-27 厦门大学 葡萄糖酸的制备方法
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
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
CN114068950B (zh) * 2020-08-03 2023-06-27 天津师范大学 基于多孔碳支撑的超细亚纳米金复合材料电催化剂及其制备方法和应用

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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
JP2005154302A (ja) * 2003-11-21 2005-06-16 Mitsubishi Gas Chem Co Inc 糖質の酸化方法

Non-Patent Citations (1)

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Title
See references of WO2008095629A1 *

Also Published As

Publication number Publication date
DE102007005528A1 (de) 2008-08-07
IL200101A0 (en) 2010-04-15
WO2008095629A1 (de) 2008-08-14
US20100137637A1 (en) 2010-06-03
CN101631610A (zh) 2010-01-20
JP2010517740A (ja) 2010-05-27
KR20090108087A (ko) 2009-10-14
BRPI0807009A2 (pt) 2014-04-22
EA200901033A1 (ru) 2010-04-30
ZA200905368B (en) 2010-10-27
WO2008095629A8 (de) 2008-10-09

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