CN104857951B - A kind of acidic oxide MoO3/MnO2/TiO2Preparation method - Google Patents
A kind of acidic oxide MoO3/MnO2/TiO2Preparation method Download PDFInfo
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- CN104857951B CN104857951B CN201510194685.2A CN201510194685A CN104857951B CN 104857951 B CN104857951 B CN 104857951B CN 201510194685 A CN201510194685 A CN 201510194685A CN 104857951 B CN104857951 B CN 104857951B
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Abstract
The invention discloses a kind of acidic oxide MoO3/MnO2/TiO2And its preparation method and application, the manganous hydroxide of preparation is mixed with titanium gel, ammonium molybdate, is calcined, acidic oxide MoO is made3/MnO2/TiO2。Raw material is cheap and easy to get, and preparation method is simple, and good catalytic activity and stability are shown in the esterification and ester exchange reaction of acid alcohol, reusable, free from environmental pollution.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of acidic oxide MoO3/MnO2/TiO2And preparation method thereof
And application.
Background technology
Carboxylic esterification is a kind of important organic chemical reactionses, and esterification products class is various and is widely used.Most commonly seen
It is to be applied to as solvent, spices, surfactant and plasticizer etc. in different chemical industries.Carboxylic acid is prepared by esterification
Ester is most common production technology, and the wherein use of catalyst has played decisive work on the yield of carboxylate and quality control
With.Traditional carboxylate esterification catalyst is mostly that mineral matter is sour, such as H2SO4, the liquid acid such as HCL, HF and HBr.Although liquid acid is honest and clean
Valency is easy to get, but shortcoming is also apparent from.Especially be particularly easy to generation environment pollution, catalyst can not reclaim, complex operation, corruption
Production equipment etc. is lost, solid catalyst can effectively solve the above problems.At present, studying and liquid is substituted using solid catalyst
The method of body acid catalyst, but apply the solid catalyst in chemical field seldom, reason is that the acid of solid catalyst contains
The shortcomings of measuring relatively low, easy in inactivation.Therefore, the key for improving the catalytic efficiency of esterification is the acid strength for improving catalyst.
The content of the invention
It is an object of the invention to provide a kind of acidic oxide MoO3/MnO2/TiO2And its preparation method and application, it is former
Expect cheap and easy to get, preparation method is simple, shown in the esterification and ester exchange reaction of acid alcohol good catalytic activity and
Stability, it is reusable, it is free from environmental pollution.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of acidic oxide MoO3/MnO2/TiO2Preparation method comprise the following steps：
1）By 1.0-2.0 grams of dispersant 5-10 milliliters, deionized water 40-60 milliliters and Manganous sulfate monohydrate mixing, room temperature
Lower magnetic agitation 12 hours, obtains solution A；
2）0.7-1.3 grams of sodium hydroxide is dissolved in deionized water, obtains solution B；
3）Solution B is added dropwise in solution A, is stirred at room temperature 12 hours；
4）Centrifugation, precipitation deionized water supersound washing 2 times, then washed 2 times with absolute ethyl alcohol, 80 DEG C of vacuum drying 12 are small
When, grinding, obtain manganous hydroxide powder；
5）By 0.2 gram of 1 gram of manganous hydroxide, 1 gram of titanium gel and ammonium molybdate mixing, grind 3 minutes, 600 DEG C are calcined 2 hours,
Grinding 10 minutes, obtains acidic oxide MoO3/MnO2/TiO2。
Described dispersant is one or both of ethylene glycol, glycerine.
Described acidic oxide MoO3/MnO2/TiO2Esterification and ester exchange reaction applied to acid alcohol.
The remarkable advantage of the present invention is：Raw material is cheap and easy to get, and preparation method is simple, is handed in the esterification and ester of acid alcohol
Change in reaction and show good catalytic activity and stability, it is reusable, it is free from environmental pollution.
Embodiment
Embodiment 1
A kind of acidic oxide MoO3/MnO2/TiO2Preparation method comprise the following steps：
1）1.0 grams of 5 milliliters of dispersant, 40 milliliters of deionized water and Manganous sulfate monohydrate are mixed, at room temperature magnetic agitation
12 hours, obtain solution A；
2）0.7 gram of sodium hydroxide is dissolved in deionized water, obtains solution B；
3）Solution B is added dropwise in solution A, is stirred at room temperature 12 hours；
4）Centrifugation, precipitation deionized water supersound washing 2 times, then washed 2 times with absolute ethyl alcohol, 80 DEG C of vacuum drying 12 are small
When, grinding, obtain manganous hydroxide powder；
5）By 0.2 gram of 1 gram of manganous hydroxide, 1 gram of titanium gel and ammonium molybdate mixing, grind 3 minutes, 600 DEG C are calcined 2 hours,
Grinding 10 minutes, obtains acidic oxide MoO3/MnO2/TiO2。
Described dispersant is ethylene glycol.
Embodiment 2
A kind of acidic oxide MoO3/MnO2/TiO2Preparation method comprise the following steps：
1）2.0 grams of 10 milliliters of dispersant, 60 milliliters of deionized water and Manganous sulfate monohydrate are mixed, at room temperature magnetic agitation
12 hours, obtain solution A；
2）1.3 grams of sodium hydroxides are dissolved in deionized water, obtain solution B；
3）Solution B is added dropwise in solution A, is stirred at room temperature 12 hours；
4）Centrifugation, precipitation deionized water supersound washing 2 times, then washed 2 times with absolute ethyl alcohol, 80 DEG C of vacuum drying 12 are small
When, grinding, obtain manganous hydroxide powder；
5）By 0.2 gram of 1 gram of manganous hydroxide, 1 gram of titanium gel and ammonium molybdate mixing, grind 3 minutes, 600 DEG C are calcined 2 hours,
Grinding 10 minutes, obtains acidic oxide MoO3/MnO2/TiO2。
Described dispersant is glycerine.
Embodiment 3
A kind of acidic oxide MoO3/MnO2/TiO2Preparation method comprise the following steps：
1）1.5 grams of 8 milliliters of dispersant, 50 milliliters of deionized water and Manganous sulfate monohydrate are mixed, at room temperature magnetic agitation
12 hours, obtain solution A；
2）1.0 grams of sodium hydroxides are dissolved in deionized water, obtain solution B；
3）Solution B is added dropwise in solution A, is stirred at room temperature 12 hours；
4）Centrifugation, precipitation deionized water supersound washing 2 times, then washed 2 times with absolute ethyl alcohol, 80 DEG C of vacuum drying 12 are small
When, grinding, obtain manganous hydroxide powder；
5）By 0.2 gram of 1 gram of manganous hydroxide, 1 gram of titanium gel and ammonium molybdate mixing, grind 3 minutes, 600 DEG C are calcined 2 hours,
Grinding 10 minutes, obtains acidic oxide MoO3/MnO2/TiO2。
Described dispersant is that volume ratio is 1:1 ethylene glycol and the mixed liquor of glycerine.
Application examples 1
By taking the esterification of ethanol and acetic acid as an example, ethanol and acetic acid, its mol ratio are added in 150mL three-neck flask
For 3:1, catalyst（Acidic oxide MoO made from embodiment 13/MnO2/TiO2）Dosage is the 1% of reactant gross mass, with band
The electric jacket of magnetic agitation heats flask to 80 DEG C, and after magnetic agitation reacts 3h, conversion ratio is reused 5 times, catalysis up to 60%
Effect is without being decreased obviously.
Application examples 2
By taking the esterification of ethanol and acetic acid as an example, ethanol and acetic acid, its mol ratio are added in 150mL three-neck flask
For 3:1, catalyst（Acidic oxide MoO made from embodiment 23/MnO2/TiO2）Dosage is the 5% of reactant gross mass, with band
The electric jacket of magnetic agitation heats flask to 95 DEG C, and after magnetic agitation reacts 6h, conversion ratio is reused 5 times, catalysis up to 90%
Effect is without being decreased obviously.
Application examples 3
By taking the esterification of ethanol and acetic acid as an example, ethanol and acetic acid, its mol ratio are added in 150mL three-neck flask
For 3:1, catalyst（Acidic oxide MoO made from embodiment 33/MnO2/TiO2）Dosage is the 3% of reactant gross mass, with band
The electric jacket of magnetic agitation heats flask to 90 DEG C, and after magnetic agitation reacts 4h, conversion ratio is reused 5 times, catalysis up to 80%
Effect is without being decreased obviously.
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, it should all belong to the covering scope of the present invention.
Claims (2)
- A kind of 1. acidic oxide MoO3/MnO2/TiO2Application, it is characterised in that：Described acidic oxide MoO3/MnO2/ TiO2Esterification and ester exchange reaction applied to acid alcohol；Its preparation method comprises the following steps：1.0-2.0 grams of dispersant 5-10 milliliters, deionized water 40-60 milliliters and Manganous sulfate monohydrate are mixed, at room temperature magnetic Power stirs 12 hours, obtains solution A；0.7-1.3 grams of sodium hydroxide is dissolved in deionized water, obtains solution B；Solution B is added dropwise in solution A, is stirred at room temperature 12 hours；Centrifugation, precipitation deionized water supersound washing 2 times, then washed 2 times with absolute ethyl alcohol, 80 DEG C are dried in vacuo 12 hours, Grinding, obtains manganous hydroxide powder；By 0.2 gram of 1 gram of manganous hydroxide, 1 gram of titanium gel and ammonium molybdate mixing, grind 3 minutes, 600 DEG C are calcined 2 hours, grind Mill 10 minutes, obtains acidic oxide MoO3/MnO2/TiO2。
- 2. the acidic oxide MoO according to claim 13/MnO2/TiO2Application, it is characterised in that：Described is scattered Agent is one or both of ethylene glycol, glycerine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394677A (en) * | 2002-08-01 | 2003-02-05 | 南京工业大学 | Multicomponent compound metal oxide solid super acidic catalyst and its preparation method |
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
| CN101126032A (en) * | 2007-09-29 | 2008-02-20 | 华中农业大学 | Method for preparing biological diesel oil by using solid acid base double-function catalyst |
| CN102826617A (en) * | 2012-09-21 | 2012-12-19 | 中国科学院过程工程研究所 | Spherical nickel hydroxide material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103466712B (en) * | 2013-08-26 | 2015-05-06 | 中信大锰矿业有限责任公司大新锰矿分公司 | Technology for preparing high-purity manganous-manganic oxide with manganous sulfate solution |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394677A (en) * | 2002-08-01 | 2003-02-05 | 南京工业大学 | Multicomponent compound metal oxide solid super acidic catalyst and its preparation method |
| CN1513767A (en) * | 2002-12-31 | 2004-07-21 | 章浩龙 | Preparation method of superfine manganese dioxide |
| CN101126032A (en) * | 2007-09-29 | 2008-02-20 | 华中农业大学 | Method for preparing biological diesel oil by using solid acid base double-function catalyst |
| CN102826617A (en) * | 2012-09-21 | 2012-12-19 | 中国科学院过程工程研究所 | Spherical nickel hydroxide material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Improvements in acidity for TiO2 and SnO2 via impregnation with MoO3 for the esterification of fatty acids;Rusiene M. de Almeida,et al;《Catalysis Communications》;20131222;第179-182页 * |
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