CN101648137A - Metal carrier load gold catalyst and application thereof in preparing aldehyde or ketone by selectively oxidizing catalytic alcohol - Google Patents
Metal carrier load gold catalyst and application thereof in preparing aldehyde or ketone by selectively oxidizing catalytic alcohol Download PDFInfo
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- CN101648137A CN101648137A CN200910195931A CN200910195931A CN101648137A CN 101648137 A CN101648137 A CN 101648137A CN 200910195931 A CN200910195931 A CN 200910195931A CN 200910195931 A CN200910195931 A CN 200910195931A CN 101648137 A CN101648137 A CN 101648137A
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Abstract
The invention discloses a metal carrier load gold catalyst and application thereof in preparing aldehyde or ketone by selectively oxidizing catalytic alcohol, wherein the catalyst is prepared by isopyknically impregnating a metal fiber or metal particle carriers with chloroauric acid or sodium chloraurate solution and baking for 2 hours at a temperature between 250 DEG C and 400 DEG C, and containing 0.5-6.0 percent of gold and 94.0-99.5 percent of carrier; in the process of preparing the aldehyde or the ketone by vapor phase selective oxydehydrogenation of the catalytic alcohol, the catalystadopts a fixed bed reaction device, takes oxygen or air as an oxidant and selectively oxidizes the alcohol to generate aldehyde or ketone under the conditions that the reaction temperature is 250-350DEG C, the weight hourly space velocity of the alcohol is 10-60<-1> hours and the mole ratio of O2 to hydroxyl group is 0.4-1.2. The catalyst has favorable heat conductivity, high low-temperature activity, good stability, low cost, high efficiency for the catalytic alcohol to prepare the aldehyde or the ketone by selective oxydehydrogenation, and environment friendliness.
Description
Technical field
The invention belongs to catalysis technical field, specifically a kind of to be carrier loaded Au catalyst and this catalyst thereof with metal prepare application in the aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation.
Technical background
Gold is considered to the chemical inertness metal always, and with respect to other noble metals such as platinum, palladiums, the catalysis potentiality of gold fail to cause enough attention always.The eighties in 20th century, people such as Japanese scientist Haruta and Britain scientist Hutchings find that nanogold particle [Nature, 2005,437,1098] has outstanding catalytic action.At present, the Au catalyst is at CO low-temperature oxidation, selective hydrogenation, NO
xReduction generates N
2With shown excellent catalytic performance in the reactions such as pure selective oxidation dehydrogenation, not only reaction condition gentleness, activity and selectivity height, good stability, and have good water-resistance, stability and humidity enhancement effect.Therefore, Au catalyst is because its excellent catalytic performance shows huge application potential in various fields.
The preparation of aldehydes or ketones is the important reaction of organic synthesis and fine chemistry industry, generally is in the presence of organic solvent, prepares with the method for stoichiometric toxic heavy metal salt oxidizing agent (as Cr salt) oxidation alcohol.Also there is aldehydes or ketones (as benzaldehyde) to prepare by the hydrolysis of organic halogen.All there are problems such as serious pollution and product poisonous component be residual in said process.The selective oxidation certain embodiments of alcohol, because do not adopt organic solvent, do not adopt poisonous and hazardous oxidant, can avoid Toxic in the product remnants of (as organic chloro thing), and efficient height, selectivity height, be an eco-friendly aldehydes or ketones building-up process.Argentum-based catalyzer has good catalytic activity and selectivity to gas phase alcohol selective oxidation dehydrogenation system aldehydes or ketones.Catalyst for electrolytic silver has been widely used in the selective oxidation certain embodiments of methyl alcohol, ethanol and ethylene glycol.Industrial catalyst for electrolytic silver cost height commonly used, the reaction temperature harshness, catalytic activity is low when being lower than 550 ℃, and can produce more accessory substance when being higher than 550 ℃, and silver micro-crystallite is reunited fast easily under hot conditions and caused catalytic activity and selectivity to descend and the increase of reaction bed resistance.Yet for higher alcohols (as phenmethylol etc.), catalyst for electrolytic silver also is not suitable for, because pyroreaction will obviously cause the pyrolysis and the over oxidation of reactant and product.
The silver catalyst catalytic alcohol oxidative dehydrogenation of oxidation carrier load generates corresponding aldehyde and much more ketone appear in the newspapers, and (US 1,067 for United States Patent (USP), 665) Bao Dao loading type silver catalyst, preparation is simple, silver-colored load capacity height, but little, the skewness of this catalyst specific area is active not ideal enough.Chinese patent (CN1262348C) adopts sol-gel process to prepare a kind of carried silver catalyst that is used for methanol dehydrogenation system anhydrous formaldehyde, after being about to a certain amount of ethyl orthosilicate and the aqueous solution that contains soluble zinc salt and aluminium salt or alcoholic solution mixing, be added drop-wise in the inorganic silver saline solution, pass through into step such as glue, aging, drying and roasting and make, but preparation process is more loaded down with trivial details, and CO is more in the accessory substance.The auri catalyst is aspect pure liquid phase oxidation, and people have done big quantity research [Science, 2006,311,362; Angew.Chem.Int.Ed.2008,47,334], more and more show the great potential of auri catalyst to pure selective oxidation.Aspect pure gas phase oxidation dehydrogenation, document [Journal of Catalysis, 2008,260:384] has been reported a kind of support type Au/SiO
2Catalyst, experiment are obtained result preferably, and the phenmethylol conversion ratio reaches 98%, and selectivity is 99%.
Above-mentioned is the loaded catalyst of carrier with the oxide, because its heat transfer property is poor, in reaction bed, easily cause hot-spot and then cause reaction bed temperature inequality that catalyst activity is reduced, be unfavorable for strong exothermal reactions such as pure gas-like phase selective oxidation dehydrogenation, so its application is restricted.Metal material has the good heat transfer performance, a small amount of domestic and foreign literature and patent report have been arranged with metallic copper alloy [Ger, 832,292], copper powder [Prom, Armenii, Sov.Nar.Khoz.Arm.SSR, Tekhn-Ekon.Byul.b (47,37～41)], albronze [Tr.Lab.Khim, Vysokomolekw.Soedin., VoronezhskUniv.3,60～2] and the dehydrogenation of copper fiber [CN.89106468.0] catalytic alcohol prepare corresponding aldehyde and ketone.CN101385972 and Catal.Commun.2009,10,1376 disclose a kind of metal micro-fiber loaded silver catalyst and uses thereof, compare with catalyst for electrolytic silver, the metallic fiber carried silver catalyst obviously reduces the reaction temperature of the gas phase selective oxidation dehydrogenation of higher alcohols, conversion ratio and selectivity obviously improve, but still not ideal enough.
Summary of the invention
The object of the present invention is to provide a kind of metal carrier load gold catalyst and this catalyst to prepare application in the aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation, its catalyst thermal conductivity is good, the low temperature active height, and the selectivity height, good stability, cost is low.
The object of the present invention is achieved like this:
A kind of metal carrier load gold catalyst, characteristics are: this catalyst is with after containing the gold chloride or sodium chloraurate solution incipient impregnation that gold is 2～10 grams per liters with metallic fiber or metallic particles carrier, made in 2 hours in 250～400 ℃ of roastings, it is 0.5-6.0% that the gained catalyst contains golden weight, contain vehicle weight is 94.0-99.5%; The material of used metallic fiber or metallic particles carrier is nickel, stainless steel, titanium, aluminium, zinc, red copper or brass; 2～150 microns of metallic fiber diameters, 2～10 millimeters of length; The metallic particles size is 0.1～1.0 millimeter.
The purposes of above-mentioned catalyst is to prepare application in the aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation; Preparing in the process of aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation, adopt fixed-bed reactor, is oxidant with oxygen or air, and reaction temperature is 250～350 ℃, and the weight (hourly) space velocity (WHSV) of alcohol is 10～60 hours
-1, O
2/ hydroxyl mol ratio is under 0.4～1.2 the condition, with alcohol optionally oxidation generate aldehydes or ketones; Wherein: the alcohol that is used to react is unit alcohol, aromatic alcohol or polyalcohol.
Technical method provided by the invention compared with prior art has following remarkable advantage:
(1), the metal carrier load gold catalyst thermal conductivity is good, the low temperature active height, the selectivity height, good stability, cost is low.
(2), the dehydrogenation of metal carrier load gold catalyst catalytic alcohol selective oxidation prepares aldehydes or ketones efficient height, environmental friendliness adopts fixed bed reactors, production cost is low.
(3), use air oxidant, cheaply be easy to get.
Description of drawings
Fig. 1 is the optical photograph of Au catalyst Au-3/S-X-Ni-8 among the embodiment 2
Fig. 2 is the SEM photo of Au catalyst Au-3/S-X-Ni-8 among the embodiment 2
Fig. 3 is the EDX photo of Au catalyst Au-3/S-X-Ni-8 among the embodiment 2
Fig. 4 is the reaction stability curve map of Au catalyst Au-3/S-X-Ni-8 catalytic phenylmethanol selective oxidation dehydrogenation producing benzaldehyde among the embodiment 2
The specific embodiment
The invention will be further elaborated below in conjunction with embodiment, and all embodiment all operate by the operating condition of technique scheme, its objective is content for a better understanding of the present invention; Therefore the cited case does not limit protection scope of the present invention.
(Applied Catalysis A 2007 328:77-82), adopts papermaking/back sintering technology, preparation sintered metal fiber carrier according to document.
Metallic fiber is: the Ni fiber that diameter is 4 microns, the Ni fiber that diameter is 8 microns, the red copper fiber that diameter is 8 microns, the red copper fiber that diameter is 80 microns, the red copper fiber that diameter is 120 microns, the brass fiber that diameter is 120 microns, the stainless steel that diameter is 8 microns (316L) fiber, the titanium fiber that diameter is 16 microns; The length of fiber is 2～5 millimeters.
The sintered metal fiber carrier that makes is expressed as S-X-Ni-4, S-X-Ni-8, S-X-Cu-Z-8, S-X-Cu-Z-80, S-X-Cu-Z-120, S-X-Cu-H-120, S-X-SS and S-X-Ti respectively.
Present embodiment provides the preparation of the carrier loaded Au catalyst of a kind of sintered metal fiber.
With S-X-Ni-8 is carrier, adopt respectively and contain golden 2 grams per liters, 4 grams per liters, 6 grams per liters, 8 grams per liters, the aqueous solution of chloraurate incipient impregnation S-X-Ni-8 carrier of 10 grams per liters, the 400 ℃ of roastings 2 hours in air of oven dry back, make the fiber-loaded Au catalyst of sintering Ni, Au content is respectively 1% (weight), 2% (weight), 3% (weight), 4% (weight) and 5% (weight), catalyst prod is designated as Au-1/S-X-Ni-8, Au-2/S-X-Ni-8, Au-3/S-X-Ni-8, Au-4/S-X-Ni-8, Au-5/S-X-Ni-8.
The optical photograph of Au-3/S-X-Ni-8 is consulted Fig. 1, ESEM (SEM) photo and power spectrum (EDX) photo and is consulted Fig. 2 and Fig. 3 respectively.
Embodiment 3
Present embodiment provides the preparation of the carrier loaded Au catalyst of sintered metal fiber.
With X-Ni-8 is carrier, the aqueous solution of chloraurate equal-volume that employing contains golden 6 grams per liters soaks the X-Ni-8 carrier, oven dry back in air 250 ℃, 350 ℃, 400 ℃, 450 ℃ of roastings, make the fiber-loaded Au catalyst of sintering Ni, be designated as Au-3-250/X-Ni-8 respectively, Au-3-350/X-Ni-8, Au-3-400/X-Ni-8, Au-3-450/X-Ni-8.
Embodiment 4
Present embodiment provides the preparation of the carrier loaded Au catalyst of sintered metal fiber.
Employing contains aqueous solution of chloraurate incipient impregnation S-X-Ni-4, S-X-Cu-Z-8, S-X-Cu-Z-80, S-X-Cu-Z-120, S-X-Cu-H-120, S-X-SS or the S-X-Ti carrier of golden 6 grams per liters, the 400 ℃ of roastings 2 hours in air of oven dry back, making Au content is 3% (weight) sintered metal fiber load type gold catalyst, be designated as Au-3/S-X-Ni-4 respectively, Au-3/S-X-Cu-Z-8, Au-3/S-X-Cu-Z-80, Au-3/S-X-Cu-Z-120, Au-3/S-X-Cu-H-120, Au-3/S-X-SS and Au-3/S-X-Ti.
Embodiment 6
Present embodiment provides the preparation of the carrier loaded Au catalyst of a kind of sintered metal fiber.
With X-Ni-8 is carrier, the sodium chloraurate aqueous solution incipient impregnation X-Ni-8 carrier, oven dry back that employing contains golden 6 grams per liters 400 ℃ of roastings 2 hours in air, making Au content is the sintered metal fiber load type gold catalyst of 3% (weight), is designated as Au-Na-3/S-X-Ni-8.
Embodiment 7
Present embodiment provides the preparation of the Au catalyst of metallic particles load.
The metallic particles carrier is: the brass of the red copper of the red copper of 0.5-1.0 millimeter, 0.3-0.5 millimeter, the red copper of 0.1-0.3 millimeter, 0.5-1.0 millimeter, the aluminium powder of 0.5-1.0 millimeter, the zinc powder of 0.5-1.0 millimeter, be expressed as F-Cu-Z-1 respectively, F-Cu-Z-2, F-Cu-Z-3, F-Cu-H, F-Al and F-Zn.
Employing contains the aqueous solution of chloraurate incipient impregnation F-Cu-Z-1 of golden 6 grams per liters, F-Cu-Z-2, F-Cu-Z-3, F-Cu-H, F-Al or F-Zn carrier, the 400 ℃ of roastings 2 hours in air of oven dry back, making Au content is 3% (weight) metal dust load type gold catalyst, is designated as Au-3/F-Cu-Z-1 respectively, Au-3/F-Cu-Z-2, Au-3/F-Cu-Z-3, Au-3/F-Cu-H, Au-3/F-Al and Au-3/F-Zn.
Embodiment 8
Present embodiment provides the preparation of metallic fiber load gold catalyst.
Metal fiber carrier is: the Ni fiber that diameter is 8 microns, the red copper fiber that red copper fiber that diameter is 8 microns and diameter are 80 microns; Fibre length 3-10 millimeter.Be designated as X-Ni-8 respectively, X-Cu-Z-8 and X-Cu-Z-80.
Employing contains the aqueous solution of chloraurate incipient impregnation X-Ni-8 of golden 6 grams per liters, X-Cu-Z-8 or X-Cu-Z-80 carrier, the 250 ℃ of roastings 2 hours in air of oven dry back, making Au content is 3% (weight) metal dust load type gold catalyst, be designated as Au-3/X-Ni-8 respectively, Au-3/X-Cu-Z-8 and Au-3/X-Cu-Z-80.
Application examples 1
Investigate the influence of the catalyst A u-3/S-X-Ni-8 catalytic performance that reaction temperature, weight (hourly) space velocity (WHSV), oxygen-methanol ratio make embodiment 2 on fixed bed reactors, used alcohol is phenmethylol, and oxygen is oxidant.Fixed bed reactors are that an internal diameter is 16 millimeters a quartz ampoule, reactant liquor pumps in the reactor with peristaltic pump, with enter beds after the oxygen mix of preheating and react, catalyst amount is 0.27 gram, volume is about 1 milliliter, and it is that 16 millimeters sintered metal fiber load gold catalyst Au-3/S-X-Ni-8 disk is stacked together for a plurality of diameters.The product chilling absorbs, and reaction condition that is adopted and yield are listed in table 1 respectively.
Be the influence of the phenmethylol gas phase selective oxidation dehydrogenation producing benzaldehyde of oxidant with oxygen on table 1 reaction temperature, weight (hourly) space velocity (WHSV) and the oxygen hydroxyl comparison Au-3/X-Ni-8 catalyst
Application examples 2
The catalytic performance of the part Au catalyst that investigation embodiment 2～3 makes on fixed bed reactors, used alcohol is phenmethylol, oxygen is oxidant.Catalyst amount is 0.27 gram, and reaction condition that is adopted and yield are listed in table 2 respectively.
Table 2 gold content and sintering temperature are to being the influence of the phenmethylol gas phase selective oxidation dehydrogenation producing benzaldehyde of oxidant with oxygen on the catalyst
Application examples 3
Investigate the catalytic performance of prepared part catalyst among the embodiment 4～8 on fixed bed reactors, used alcohol is phenmethylol, and oxygen, air are oxidant.Catalyst amount is 0.27 gram, and reaction condition that is adopted and yield are listed in table 3 respectively.
Table 3 is with the reaction result of phenmethylol gas phase selective oxidation dehydrogenation producing benzaldehyde on the Au catalyst of different metal preparing carriers
Application examples 4
On fixed bed reactors, investigate the low-carbon alcohols gas-like phase selective oxidation dehydrogenation reaction catalytic performance of embodiment 1 prepared catalyst A u-3/S-X-Ni-8, used alcohol is 1,2-propane diols, cyclohexanol, 1-octanol, sec-n-octyl alcohol, 1-benzyl carbinol, 2 phenylethyl alcohol etc., oxygen is oxidant.Reaction condition that is adopted and yield are listed in table 4 respectively.
The gas phase selective oxidation dehydrogenation reaction result of several alcohol on the table 4Au-3/S-X-Ni-8 catalyst
Application examples 5
Investigate the reaction stability of embodiment 2 made catalyst A u-3/X-Ni-8 on fixed bed reactors, used alcohol is phenmethylol.Reaction condition is: 280 ℃ of reaction temperatures, and catalyst amount 0.27 gram, volume is about 1 milliliter, and it is that 16 millimeters Au-3/X-Ni-8 catalyst disks are stacked together for a plurality of diameters, weight (hourly) space velocity (WHSV) 20 hours
-1, oxygen/hydroxyl is than 0.6, and the product chilling absorbs, and reaction result is illustrated in Fig. 4.
Comparative Examples
According to CN101385972 and document [Catal.Commun.2009,10,1376] disclosed method, be preparing carriers with S-X-Ni-8 the Ag load capacity be the catalyst of 10% (weight), the roasting 4 hours in 600 ℃ of air of this catalyst is designated as Ag/S-X-Ni-8.
Reactivity worth at the phenmethylol selective oxidation dehydrogenation producing benzaldehyde under the differential responses temperature of investigating Comparative Examples catalyst A g/S-X-Ni-8 on the fixed bed reactors the results are shown in Table 5.Catalyst amount is 0.27 gram, and oxygen is oxidant, and the oxygen hydroxyl is than 0.6, pure WHSV=20 hour
-1In addition, under 380 ℃ reaction temperature, the stability of catalyst is investigated, the reaction result of differential responses time is also listed in table 5.
Table 5 Comparative Examples catalyst A g/X-Ni-8 goes up phenylmethanol gas phase selective oxidation dehydrogenation producing benzaldehyde reaction result
| Reaction temperature (℃) | Reaction time (h) | Selectivity (%) | Conversion ratio (%) | Yield (%) |
| ??250 | ??1 | ??96 | ??23 | ??22 |
| ??300 | ??1 | ??97 | ??30 | ??29 |
| ??330 | ??1 | ??91 | ??49 | ??45 |
| ??350 | ??1 | ??88 | ??70 | ??62 |
| ??380 | ??1 | ??86 | ??91 | ??78 |
| ??400 | ??1 | ??85 | ??94 | ??80 |
| ??380 | ??15 | ??86 | ??90 | ??77 |
| ??380 | ??20 | ??85 | ??88 | ??75 |
| ??380 | ??23 | ??85 | ??82 | ??70 |
| ??380 | ??25 | ??83 | ??75 | ??62 |
Au-3/S-X-Ni-8 catalyst of the present invention is compared with the disclosed Ag catalyst of CN101385972 (Comparative Examples catalyst), activity/selectivity height not only, and also reaction stability is good.
Claims (3)
1, a kind of metal carrier load gold catalyst, it is characterized in that this catalyst is with after containing the gold chloride or sodium chloraurate solution incipient impregnation that gold is 2～10 grams per liters with metallic fiber or metallic particles carrier, made in 2 hours in 250～400 ℃ of roastings, it is 0.5-6.0% that the gained catalyst contains golden weight, contain vehicle weight is 94.0-99.5%; The material of used metallic fiber or metallic particles carrier is nickel, stainless steel, titanium, aluminium, zinc, red copper or brass; 2～150 microns of metallic fiber diameters, 2～10 millimeters of length; The metallic particles size is 0.1～1.0 millimeter.
2, the purposes of the described catalyst of a kind of claim 1 is characterized in that this catalyst prepares application in the aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation.
3, purposes according to claim 2, it is characterized in that preparing in the process of aldehydes or ketones in the dehydrogenation of catalytic alcohol gas phase selective oxidation, adopt fixed-bed reactor, is oxidant with oxygen or air, reaction temperature is 250～350 ℃, and the weight (hourly) space velocity (WHSV) of alcohol is 10～60 hours
-1, O
2/ hydroxyl mol ratio is under 0.4～1.2 the condition, with alcohol optionally oxidation generate aldehydes or ketones; Wherein: the alcohol that is used to react is unit alcohol, aromatic alcohol or polyalcohol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921475A (en) * | 2012-08-03 | 2013-02-13 | 北京化工大学 | Sheet-shaped or polyhedron-shaped supported silver catalyst and preparation method thereof |
| CN103272593A (en) * | 2013-06-14 | 2013-09-04 | 华东师范大学 | Load-type nano-porous gold catalyst as well as preparation method and application thereof |
| CN103801275A (en) * | 2014-03-10 | 2014-05-21 | 济南大学 | Preparation method of palladium coating solid-phase micro-extraction fiber |
| CN104001556A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | High-thermal conductivity eggshell type catalyst carrier and preparation method and application |
| CN105289649A (en) * | 2014-05-28 | 2016-02-03 | 易高环保能源研究院有限公司 | Metal-phase carrier-loaded type catalyst, and preparation method and application thereof |
| CN109985622A (en) * | 2019-05-10 | 2019-07-09 | 中国石油大学(华东) | One kettle way prepares γ-Al2O3The Au-Pd catalyst of load |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6814356A (en) * | 1967-10-17 | 1969-04-21 | ||
| CN101385972A (en) * | 2008-10-31 | 2009-03-18 | 华东师范大学 | Metal micro-fiber loaded silver catalyst and use thereof |
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2009
- 2009-09-18 CN CN2009101959310A patent/CN101648137B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921475A (en) * | 2012-08-03 | 2013-02-13 | 北京化工大学 | Sheet-shaped or polyhedron-shaped supported silver catalyst and preparation method thereof |
| CN103272593A (en) * | 2013-06-14 | 2013-09-04 | 华东师范大学 | Load-type nano-porous gold catalyst as well as preparation method and application thereof |
| CN103801275A (en) * | 2014-03-10 | 2014-05-21 | 济南大学 | Preparation method of palladium coating solid-phase micro-extraction fiber |
| CN105289649A (en) * | 2014-05-28 | 2016-02-03 | 易高环保能源研究院有限公司 | Metal-phase carrier-loaded type catalyst, and preparation method and application thereof |
| CN105289649B (en) * | 2014-05-28 | 2022-03-15 | 易高环保能源研究院有限公司 | Metal phase carrier supported catalyst and preparation method and application thereof |
| CN104001556A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | High-thermal conductivity eggshell type catalyst carrier and preparation method and application |
| CN104001556B (en) * | 2014-06-10 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | A kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application |
| CN109985622A (en) * | 2019-05-10 | 2019-07-09 | 中国石油大学(华东) | One kettle way prepares γ-Al2O3The Au-Pd catalyst of load |
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