CN104841419B - MoO3/ZnO/TiO2Solid acid catalyst and preparation method thereof - Google Patents
MoO3/ZnO/TiO2Solid acid catalyst and preparation method thereof Download PDFInfo
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- CN104841419B CN104841419B CN201510194601.5A CN201510194601A CN104841419B CN 104841419 B CN104841419 B CN 104841419B CN 201510194601 A CN201510194601 A CN 201510194601A CN 104841419 B CN104841419 B CN 104841419B
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Abstract
The invention discloses a kind of MoO3/ZnO/TiO2Solid acid catalyst and preparation method thereof, it is the solution A that will be formed by dispersant, deionized water, zinc nitrate hexahydrate, after being mixed with the solution B of sodium hydroxide, deionized water formation, separating, washing, drying, grinding obtain zinc hydroxide powder, then it mix with titanium gel, ammonium molybdate, ground, be calcined after obtain the MoO3/ZnO/TiO2Solid acid catalyst.Raw material of the present invention is cheap and easy to get, preparation method simple, and obtained solid acid catalyst acid strength is high, and good catalytic activity and stability is shown in the esterification and ester exchange reaction of acid alcohol, and reusable, free from environmental pollution.
Description
Technical field
The invention belongs to catalyst material technical field, and in particular to a kind of MoO3/ZnO/TiO2Solid acid catalyst and its
Preparation method.
Background technology
Carboxylic esterification is the important organic chemical reactionses of a class, and esterification products species is various, be widely used, frequently as molten
Agent, spices, surfactant and plasticizer etc. are applied in different chemical industries, and it is most to prepare carboxylate by esterification
The use of universal production technology, wherein catalyst plays conclusive effect on the yield of carboxylate and quality control.
Traditional carboxylate esterification catalyst is generally mineral matter liquid acid, such as H2SO4, HCL, HF and HBr etc..Although liquid acid is cheap and easy to get,
But its shortcoming is it is also obvious that especially catalyst can not reclaim, be particularly easy to pollute environment, and complex operation, perishable production
Equipment, can effectively be solved the above problems using solid acid catalyst.At present, although liquid is substituted using solid acid catalyst
The research report of body acid catalyst, but it is still seldom in chemical field applying solid acid catalyst, and reason is solid acid catalysis
Agent has the shortcomings that acid content is relatively low, easy in inactivation.Therefore, the key for improving esterification catalytic efficiency is that improving solid acid urges
The acid strength of agent.
The content of the invention
It is an object of the invention to provide a kind of MoO3/ZnO/TiO2Solid acid catalyst and preparation method thereof, gained solid
Acid catalyst acid strength is high, and good catalytic activity and stably is shown in the esterification and ester exchange reaction of acid alcohol
Property, and can overcome liquid acid catalyst can not reclaim, easily pollute environment shortcoming, realize the reuse of catalyst.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of MoO3/ZnO/TiO2Solid acid catalyst, its preparation method comprises the following steps：
1）5-10ml dispersants, 40-60ml deionized waters and 2.5-3.5g zinc nitrate hexahydrates are added into reaction successively to hold
In device, magnetic agitation formation solution A stirs 12h at room temperature；
2）0.7-1.3g sodium hydroxides are dissolved in 50ml deionized waters and form solution B；
3）Solution B is added dropwise in solution A, at room temperature stirring reaction 12 hours；
4）Precipitation is centrifuged, gained supersound washing 2 times in deionized water are deposited in, then washed 2 times with absolute ethyl alcohol；
5）Gained solid is deposited in 80 DEG C of vacuum drying box and dried 12 hours, and zinc hydroxide powder is obtained after grinding；
6）1g zinc hydroxides powder, 1g titanium gels, 0.2g ammonium molybdates are sequentially placed into ball mill and mixes, grind 3 minutes,
Then in 600 DEG C of Muffle kiln roastings 2 hours, then ground 10 minutes with agate mortar, obtain the MoO3/ZnO/TiO2Solid
Acid catalyst.
The dispersant is one or both of ethylene glycol, glycerine.
The MoO3/ZnO/TiO2Solid acid catalyst is applied to the esterification and ester exchange reaction of catalysis acid alcohol.
The remarkable advantage of the present invention is：Raw material of the present invention is cheap and easy to get, preparation method simple, obtained solid acid catalysis
Agent acid strength is high, and good catalytic activity and stability is shown in the esterification and ester exchange reaction of acid alcohol, and can
Reuse, recycle 5 catalytic activity without being decreased obviously, overcoming liquid acid catalyst can not reclaim, easily pollute environment
Shortcoming, have a good application prospect.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
A kind of MoO3/ZnO/TiO2Solid acid catalyst, its preparation method comprises the following steps：
1）5ml ethylene glycol, 40ml deionized waters and 2.5g zinc nitrate hexahydrates are added in reaction vessel successively, magnetic force is stirred
Mix to form solution A, 12h is stirred at room temperature；
2）0.7g sodium hydroxides are dissolved in 50ml deionized waters and form solution B；
3）Solution B is added dropwise in solution A, at room temperature stirring reaction 12 hours；
4）Precipitation is centrifuged, gained supersound washing 2 times in deionized water are deposited in, then washed 2 times with absolute ethyl alcohol；
5）Gained solid is deposited in 80 DEG C of vacuum drying box and dried 12 hours, and zinc hydroxide powder is obtained after grinding；
6）1g zinc hydroxides powder, 1g titanium gels, 0.2g ammonium molybdates are sequentially placed into ball mill and mixes, grind 3 minutes,
Then in 600 DEG C of Muffle kiln roastings 2 hours, then ground 10 minutes with agate mortar, obtain the MoO3/ZnO/TiO2Solid
Acid catalyst.
By taking the esterification of ethanol and acetic acid as an example, the amount that material is added in 150mL three-neck flask is 3:1 ethanol
And acetic acid, add gained MoO3/ZnO/TiO2Solid acid catalyst, catalyst amount is the 1% of reactant gross mass, with band magnetic
Flask is heated to 80 DEG C by the electric jacket of power stirring, and starts magnetic agitation, reacts and conversion ratio is determined after 6h up to 60%.
Embodiment 2
A kind of MoO3/ZnO/TiO2Solid acid catalyst, its preparation method comprises the following steps：
1）8ml glycerine, 50ml deionized waters and 3g zinc nitrate hexahydrates are added in reaction vessel successively, magnetic agitation
Solution A is formed, 12h is stirred at room temperature；
2）1.0g sodium hydroxides are dissolved in 50ml deionized waters and form solution B；
3）Solution B is added dropwise in solution A, at room temperature stirring reaction 12 hours；
4）Precipitation is centrifuged, gained supersound washing 2 times in deionized water are deposited in, then washed 2 times with absolute ethyl alcohol；
5）Gained solid is deposited in 80 DEG C of vacuum drying box and dried 12 hours, and zinc hydroxide powder is obtained after grinding；
6）1g zinc hydroxides powder, 1g titanium gels, 0.2g ammonium molybdates are sequentially placed into ball mill and mixes, grind 3 minutes,
Then in 600 DEG C of Muffle kiln roastings 2 hours, then ground 10 minutes with agate mortar, obtain the MoO3/ZnO/TiO2Solid
Acid catalyst.
By taking the esterification of ethanol and acetic acid as an example, the amount that material is added in 150mL three-neck flask is 3:1 ethanol
And acetic acid, add gained MoO3/ZnO/TiO2Solid acid catalyst, catalyst amount is the 3% of reactant gross mass, with band magnetic
Flask is heated to 95 DEG C by the electric jacket of power stirring, and starts magnetic agitation, reacts and conversion ratio is determined after 3h up to 87%.
Embodiment 3
A kind of MoO3/ZnO/TiO2Solid acid catalyst, its preparation method comprises the following steps：
1）10ml is pressed 1 by ethylene glycol and glycerine successively:1（v/v）Dispersant, 60ml deionized waters and the 3.5g of mixing
Zinc nitrate hexahydrate is added in reaction vessel, magnetic agitation formation solution A, and 12h is stirred at room temperature；
2）1.3g sodium hydroxides are dissolved in 50ml deionized waters and form solution B；
3）Solution B is added dropwise in solution A, at room temperature stirring reaction 12 hours；
4）Precipitation is centrifuged, gained supersound washing 2 times in deionized water are deposited in, then washed 2 times with absolute ethyl alcohol；
5）Gained solid is deposited in 80 DEG C of vacuum drying box and dried 12 hours, and zinc hydroxide powder is obtained after grinding；
6）1g zinc hydroxides powder, 1g titanium gels, 0.2g ammonium molybdates are sequentially placed into ball mill and mixes, grind 3 minutes,
Then in 600 DEG C of Muffle kiln roastings 2 hours, then ground 10 minutes with agate mortar, obtain the MoO3/ZnO/TiO2Solid
Acid catalyst.
By taking the esterification of ethanol and acetic acid as an example, the amount that material is added in 150mL three-neck flask is 3:1 ethanol
And acetic acid, add gained MoO3/ZnO/TiO2Solid acid catalyst, catalyst amount is the 5% of reactant gross mass, with band magnetic
Flask is heated to 90 DEG C by the electric jacket of power stirring, and starts magnetic agitation, reacts and conversion ratio is determined after 4h up to 90%.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (2)
1. a kind of MoO3/ZnO/TiO2Application of the solid acid catalyst in catalysis acid alcohol esterification, it is characterised in that：It is described
MoO3/ZnO/TiO2The preparation method of solid acid catalyst comprises the following steps：
1）5-10ml dispersants, 40-60ml deionized waters and 2.5-3.5g zinc nitrate hexahydrates are stirred to form solution A, room temperature
Lower stirring 12h；
2）0.7-1.3g sodium hydroxides are dissolved in 50ml deionized waters and form solution B；
3）Solution B is added dropwise in solution A, at room temperature stirring reaction 12 hours；
4）Precipitation is centrifuged, gained supersound washing 2 times in deionized water are deposited in, then washed 2 times with absolute ethyl alcohol；
5）Gained solid is deposited in 80 DEG C and dried 12 hours, and zinc hydroxide powder is obtained after grinding；
6）1g zinc hydroxides powder, 1g titanium gels, 0.2g ammonium molybdates are mixed, ground 3 minutes, it is then small in 600 DEG C of roastings 2
When, then grind 10 minutes, obtain MoO3/ZnO/TiO2Solid acid catalyst.
2. MoO according to claim 13/ZnO/TiO2Application of the solid acid catalyst in catalysis acid alcohol esterification, its
It is characterised by：The dispersant is one or both of ethylene glycol, glycerine.
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| CN1546235A (en) * | 2003-12-09 | 2004-11-17 | 南开大学 | Novel catalyst for synthesizing tertiary-butyl substituted benzene phenols and its preparation process |
| CN1314654C (en) * | 2005-04-05 | 2007-05-09 | 天津大学 | Method for synthesizing phenyloxalate from dicthyl oxalate and phenol |
| CN101905155A (en) * | 2009-06-08 | 2010-12-08 | 常州化学研究所 | Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof |
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