CN103894192B - A kind of preparation of load type gold silver alloy catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl formate and application thereof - Google Patents
A kind of preparation of load type gold silver alloy catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl formate and application thereof Download PDFInfo
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- CN103894192B CN103894192B CN201410156809.3A CN201410156809A CN103894192B CN 103894192 B CN103894192 B CN 103894192B CN 201410156809 A CN201410156809 A CN 201410156809A CN 103894192 B CN103894192 B CN 103894192B
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Abstract
The invention provides a kind of electrum catalyst of titanium dichloride load preparation method and under gas phase condition the operating condition of photocatalysis partial oxidation preparation of methyl formate from methanol.With the mixed phase titanium dioxide of Detitanium-ore-type or anatase and a small amount of rutile for carrier, with solubility gold salt and soluble silver salt for presoma, take sodium borohydride as reducing agent, prepare the electrum catalyst of titanium dichloride load, this catalyst, can by methanol gas partial oxidation formic acid methyl esters in oxygen-containing atmosphere under UV-irradiation.Prepared catalyst has good stability, and methanol conversion is high, the selective high feature of methyl formate.
Description
Technical field
The present invention relates to a kind of preparation and application thereof of photochemical catalyst, belong to derived energy chemical and field of fine chemical, under being mainly applicable to low temperature, gas-phase photocatalysis partial oxidation Methanol methyl formate reacts, and provides preparation method and the catalytic reaction condition of catalyst.
Background technology
Methyl formate is described as " omnipotent chemical intermediate ", can be used for producing formic acid, formamide and other tens kinds of chemical products, also directly pesticide, bactericide, fumigant, agent for tobacco treatment and gasoline additive [G.Jenner.Appl.Catal.A.1995 can be used as, 121,25-44].
Traditional methyl formate production method mainly contains methanol esterification method, methanol carbonylation, methanol dehydrogenation method and one-step method from syngas, and wherein methanol dehydrogenation method comprises methyl alcohol direct dehydrogenation and oxidative dehydrogenation two kinds of methods.Esterification process technique is backward, production cost is high, equipment corrosion is serious, and production technology is substantially superseded; Carbonylation method reaction pressure high (4.0MPa), complex process, catalyst sodium methoxide facile hydrolysis blocking pipeline and production cost is high; One-step method from syngas reaction pressure high (U.S. is greater than 0.69MPa, domestic 4.0-5.0MPa).
Compared with other conventional methods, traditional methanol dehydrogenation method has that raw material is single, reaction condition is gentle, reaction selectivity and the advantage such as activity is high, equipment investment is low, is thus subject to extensive concern.But conventional catalyst optimal reaction temperature higher (about 280 DEG C), can not meet the requirement of low energy consumption.
Other catalyst are as ruthenium [H.Liu, etal.J.Phys.Chem.B2005,109,2155-2163.], palladium [J.Lichtenberger, etal.Phys.Chem.Chem.Phys.2007,9,4902 – 4906] although reaction temperature is lower, expensive.
[the H.Kominami such as H.Kominami, etal.Chem.Comm.2010,11,426-429.] report use anatase titanium dioxide achieve under ultraviolet light conditions from methyl alcohol to methyl formate gas phase oxidation dehydrogenation reaction, under room temperature, (25 DEG C) methyl formate conversion ratio nearly 10%, selective more than 91%.The report such as Yang Xuzhuan utilizes the silver catalyst of load under liquid-phase condition, realize the conversion [XuzhuangYang, etal.CatalysisCommunications.2014,43,192-196] of methyl alcohol to methyl formate.
Summary of the invention
Object of the present invention mainly provides a kind of reaction temperature at 10-80 DEG C, can by the electrum AuAg-TiO of the highly efficient titania load of methanol fractions oxidation methyl formate processed under gas phase and illumination condition
2photochemical catalyst preparation method and application.
The present invention is first by AuAg-TiO
2photochemical catalyst is used for the reaction of methanol vapor phase photocatalysis partial oxidation methyl formate.Experimental result shows, catalyst there is higher methanol conversion and methyl formate selective.Within the scope of experimental temperature and under illumination condition, methanol conversion reaches more than 80-85%, and methyl formate is selective reaches more than 85-98%.
Catalyst A uAg-TiO of the present invention
2electrum and 90-99%(mol ratio by 1-10%) titanium dioxide form, titanium dioxide crystal form is that Detitanium-ore-type or anatase and a small amount of (lower than 25%) rutile mixed phase are formed.
Preparation method of the present invention adopts metal replacement legal system standby.
Preparation method is as follows:
(1) get a certain amount of soluble silver salt and solubility gold salt, be all configured to the solution of 0.005mol/L with distilled water;
(2) with Ag:NaBH
4=5:6(mol ratio) take appropriate sodium borohydride, be dissolved in the distilled water of ice bath cooling in advance.Take a certain amount of titanium dioxide ultrasonic disperse in above-mentioned sodium borohydride aqueous solution;
(3) under keeping ice bath cooling to continue to stir the silver nitrate aqueous solution that step (1) is prepared dropwise added in the mixed solution that step (2) obtains.Be added dropwise to complete rear continuation and stir 30min.Stop stirring and leave standstill 24h;
(4) after centrifugal removing supernatant, the solid obtained is scattered in distilled water again, under constantly stirring, dropwise adds the solubility gold solution that appropriate step (1) configures, continue to stir 30min;
(5) centrifugation, with concentrated ammonia liquor, distilled water, ethanol washing, dry at 50 DEG C, obtain catalyst after 400 DEG C of calcining 1h.
The specific area of specific surface area of catalyst prepared by the present invention and titanium dioxide precursor is close, generally at 50-300m
2/ g.
Titanium dioxide as above can be the mixed phase titanium dioxide of commercial mixed phase titanium dioxide P25, commercial anatase titanium dioxide ST-01 or self-control Detitanium-ore-type or anatase and rutile.
Soluble silver salt as above can be silver nitrate, silver acetate, silver perchlorate, silver fluoride, and solubility gold salt can be gold chloride, acetic acid gold.
Catalyst application of the present invention is as follows in gas-phase methanol photocatalysis partial oxidation methyl formate reaction method:
Catalyst fines spraying on a solid surface, this solid can be glass, stainless steel, plastics, pottery, light source is ultraviolet light or sunshine, reaction temperature is 10-80 DEG C, methyl alcohol/oxygen mole ratio is 1-6, methyl alcohol volumn concentration 1-3%, nitrogen is Balance Air, and reaction velocity is 100-400l ﹒ g
-1﹒ h
-1.
Compared with the prior art the present invention has following innovation and feature:
First by AuAg-TiO
2catalyst is used for gas-phase photocatalysis methanol fractions oxidation methyl formate reaction processed;
Catalytic reaction temperature is 10-80 DEG C, is reaction temperature minimum operation condition in current methanol gas-phase oxidation methyl formate technique.
accompanying drawing illustrates:
Fig. 1 is the AuAg-TiO of preparation
2solid uv-vis spectra (UV-Vis) figure of photochemical catalyst;
Fig. 2 is the AuAg-TiO of preparation
2x-ray diffraction (XRD) collection of illustrative plates of photochemical catalyst;
Fig. 3 is the AuAg-TiO of preparation
2transmission electron microscope (TEM) figure of photochemical catalyst.
detailed description of the invention:
Below in conjunction with embodiment, the present invention is further illustrated, the present invention includes but be not limited to the following examples.
Take 0.0145gNaBH
4, be dissolved in the distilled water of 100ml ice bath cooling in advance, taken 0.5gP25 titania powder ultrasonic disperse in above-mentioned solution.Dropwise add 64ml0.005mol/lAgNO with vigorous stirring
3the aqueous solution continues to stir 30min, stops stirring and leaves standstill 24h, centrifugation, and removing supernatant, is scattered in the solid obtained in distilled water again, and dropwise adds the HAuCl of 16ml0.005mol/l under constantly stirring
4solution, continues to stir 30min.Centrifugation, with concentrated ammonia liquor, distilled water, ethanol washing, vacuum drying 6h at 50 DEG C, calcines 1h at 400 DEG C and namely obtains 2.56%AuAg-TiO
2photochemical catalyst.In a similar manner, change and add the amount of P25 and the amount of gold chloride and liquor argenti nitratis ophthalmicus, the AuAg-TiO of different mol ratio and different gold and silver ratio can be prepared
2catalyst.
2.56%AuAg-TiO prepared by said method
2the substrate of glass scribbling catalyst on the glass substrate, and is placed in photo catalysis reactor by photochemical catalyst spraying, passes into reactor feed gas and open uviol lamp to start reaction, utilizes gas chromatographic detection product composition.Catalyst amount 0.02g, reaction temperature 10-80
oc, unstripped gas forms 1% methyl alcohol, 0.5% oxygen, 98.5% nitrogen, raw gas flow 50ml/min, air speed 150l ﹒ g
-1﹒ h
-1.
Above catalyst carries out the display of photocatalysis performance evaluation result, and the methanol conversion of this catalyst is up to 90%, and the selective of methyl formate is up to more than 95%.This catalyst is to methanol conversion and the selective height of methyl formate, and reaction stability is good, is excellent photochemical catalytic oxidation Methanol methyl formate catalyst.
Claims (1)
1. the method for a gas-phase photocatalysis partial oxidation preparation of methyl formate from methanol, it is characterized in that catalyst is the electrum of titanium dichloride load, titanium dioxide and electrum particle are active component, titanium dioxide be Detitanium-ore-type or anatase and content lower than 25% the mixed phase structure of rutile, the total molar fraction of electrum is 1-10%, and gold and silver ratio is 1:5-5:1; The preparation of catalyst adopts gold and silver displacement method, take titanium dioxide as carrier, in the sodium borohydride aqueous solution of ice bath cooling, add titanium dioxide in appropriate and uses ultrasonic mixing, the silver soluble saline solution of appropriate 0.005mol/L is dropwise added under constantly stirring, be added dropwise to complete rear stopping to stir and leave standstill centrifugation after 24h, with distilled water, ethanol washing, obtain Ag-TiO
2pressed powder, by the Ag-TiO obtained
2pressed powder is scattered in distilled water again, dropwise add the solubility gold saline solution of appropriate 0.005mol/L under stirring, after continuing to stir 0.5h, centrifugation also uses the washing of concentrated ammonia liquor, distilled water, ethanol for several times, dry at 50 DEG C, at 400 DEG C, calcining obtains AuAg-TiO in 1 hour
2photochemical catalyst; The reaction of gas-phase photocatalysis partial oxidation preparation of methyl formate from methanol is carried out under UV-irradiation, and reaction temperature is 10-80 DEG C, and in unstripped gas, methyl alcohol volume content is 1-3%, and methyl alcohol/oxygen molar ratio is CH
3oH:O
2=1:1-6:1, Balance Air is nitrogen, air speed 100-400L ﹒ g
-1﹒ h
-1.
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| CN201410156809.3A CN103894192B (en) | 2014-04-18 | 2014-04-18 | A kind of preparation of load type gold silver alloy catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl formate and application thereof |
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| CN201410156809.3A CN103894192B (en) | 2014-04-18 | 2014-04-18 | A kind of preparation of load type gold silver alloy catalyst of gas-phase photocatalysis selective oxidation methanol-fueled CLC methyl formate and application thereof |
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| CN103894192B true CN103894192B (en) | 2016-01-27 |
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| CN107056614A (en) * | 2017-03-28 | 2017-08-18 | 内蒙古大学 | A kind of preparation of electrum catalyst and its method for disposably synthesizing a variety of esters for gas-phase photocatalysis methanol and ethanol |
| CN106883088A (en) * | 2017-03-30 | 2017-06-23 | 内蒙古大学 | A kind of electrum catalyst preparation and its for the method for gas-phase photocatalysis ethanol synthesizing ethylene, acetaldehyde and acetone |
| CN106883124A (en) * | 2017-03-30 | 2017-06-23 | 内蒙古大学 | A kind of preparation of silver catalyst and its method for disposably synthesizing various esters for gas-phase photocatalysis ethanol and methyl alcohol |
| CN107032993A (en) * | 2017-05-09 | 2017-08-11 | 内蒙古大学 | A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters |
Citations (3)
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|---|---|---|---|---|
| CN101985103A (en) * | 2010-07-26 | 2011-03-16 | 北京大学 | Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof |
| CN102935364A (en) * | 2012-11-13 | 2013-02-20 | 福州大学 | Supported bimetallic catalyst for CO catalytic oxidation through visible light at room temperature |
| CN103191731A (en) * | 2013-03-26 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985103A (en) * | 2010-07-26 | 2011-03-16 | 北京大学 | Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof |
| CN102935364A (en) * | 2012-11-13 | 2013-02-20 | 福州大学 | Supported bimetallic catalyst for CO catalytic oxidation through visible light at room temperature |
| CN103191731A (en) * | 2013-03-26 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface;Bingjun Xu等;《Chem. Eur. J.》;20140313;第20卷;摘要，实验部分，结论部分 * |
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