CN104857951A - Preparation method of acidic oxide MoO3 / MnO / TiO2 - Google Patents
Preparation method of acidic oxide MoO3 / MnO / TiO2 Download PDFInfo
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- CN104857951A CN104857951A CN201510194685.2A CN201510194685A CN104857951A CN 104857951 A CN104857951 A CN 104857951A CN 201510194685 A CN201510194685 A CN 201510194685A CN 104857951 A CN104857951 A CN 104857951A
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- acidic oxide
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Abstract
The invention discloses an acidic oxide MoO3 / MnO / TiO2 and a preparation method and application thereof. The prepared manganese hydroxide is mixed and roasted with titanium gel and ammonium molybdate to prepare the acidic oxide MoO3 / MnO / TiO2. The raw materials are cheap and readily available; the preparation method is simple; and the acidic oxide MoO3 / CuO / TiO2 shows good catalytic activity and stability in acid and alcohol esterification and transesterification reaction, can be reused, and does not pollute the environment.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of acidic oxide MoO
3/ MnO
2/ TiO
2and its preparation method and application.
Background technology
Carboxylic esterification is the important organic chemical reactions of a class, and esterification products class is various and be widely used.The most commonly be applied in different chemical industry as solvent, spices, surfactant and plasticizer etc.Preparing carboxylate by esterification is the most general production technology, and wherein the use of catalyst has played decisive role on the productive rate and quality control of carboxylate.Traditional carboxylate esterification catalyst mostly is mineral matter acid, as H
2sO
4, the liquid acid such as HCL, HF and HBr.Although liquid acid is cheap and easy to get, shortcoming also clearly.Especially especially easily produce environmental pollution, catalyst can not reclaim, complicated operation, corrosion production equipment etc., solid catalyst can effectively solve the problem.At present, studying the method adopting solid catalyst to substitute liquid acid catalyst, but the solid catalyst being applied in chemical field is little, reason is the shortcomings such as the acid content of solid catalyst is lower, easy in inactivation.Therefore, the key improving the catalytic efficiency of esterification is the acid strength improving catalyst.
Summary of the invention
The object of the present invention is to provide a kind of acidic oxide MoO
3/ MnO
2/ TiO
2and its preparation method and application, cheaper starting materials is easy to get, and preparation method is simple, in the esterification and ester exchange reaction of acid alcohol, show good catalytic activity and stability, reusable, free from environmental pollution.
For achieving the above object, the present invention adopts following technical scheme:
A kind of acidic oxide MoO
3/ MnO
2/ TiO
2preparation method comprise the following steps:
1) by dispersant 5-10 milliliter, deionized water 40-60 milliliter and Manganous sulfate monohydrate 1.0-2.0 gram of mixing, room temperature lower magnetic force stirs 12 hours, obtains solution A;
2) 0.7-1.3 gram of NaOH is dissolved in deionized water, obtains solution B;
3) solution B is dropwise joined in solution A, stirring at room temperature 12 hours;
4) centrifugal, precipitate with deionized water supersound washing 2 times, then use absolute ethanol washing 2 times, 80 DEG C of vacuum drying 12 hours, grinding, obtains manganous hydroxide powder;
5) by manganous hydroxide 1 gram, titanium gel 1 gram and ammonium molybdate 0.2 gram mixing, grinding 3 minutes, 600 DEG C of roastings 2 hours, grind 10 minutes, obtain acidic oxide MoO
3/ MnO
2/ TiO
2.
Described dispersant is one or both in ethylene glycol, glycerine.
Described acidic oxide MoO
3/ MnO
2/ TiO
2be applied to esterification and the ester exchange reaction of acid alcohol.
Remarkable advantage of the present invention is: cheaper starting materials is easy to get, and preparation method is simple, in the esterification and ester exchange reaction of acid alcohol, show good catalytic activity and stability, reusable, free from environmental pollution.
Detailed description of the invention
embodiment 1
A kind of acidic oxide MoO
3/ MnO
2/ TiO
2preparation method comprise the following steps:
1) by dispersant 5 milliliters, deionized water 40 milliliters and Manganous sulfate monohydrate 1.0 grams mixing, room temperature lower magnetic force stirs 12 hours, obtains solution A;
2) 0.7 gram of NaOH is dissolved in deionized water, obtains solution B;
3) solution B is dropwise joined in solution A, stirring at room temperature 12 hours;
4) centrifugal, precipitate with deionized water supersound washing 2 times, then use absolute ethanol washing 2 times, 80 DEG C of vacuum drying 12 hours, grinding, obtains manganous hydroxide powder;
5) by manganous hydroxide 1 gram, titanium gel 1 gram and ammonium molybdate 0.2 gram mixing, grinding 3 minutes, 600 DEG C of roastings 2 hours, grind 10 minutes, obtain acidic oxide MoO
3/ MnO
2/ TiO
2.
Described dispersant is ethylene glycol.
embodiment 2
A kind of acidic oxide MoO
3/ MnO
2/ TiO
2preparation method comprise the following steps:
1) by dispersant 10 milliliters, deionized water 60 milliliters and Manganous sulfate monohydrate 2.0 grams mixing, room temperature lower magnetic force stirs 12 hours, obtains solution A;
2) 1.3 grams of NaOH are dissolved in deionized water, obtain solution B;
3) solution B is dropwise joined in solution A, stirring at room temperature 12 hours;
4) centrifugal, precipitate with deionized water supersound washing 2 times, then use absolute ethanol washing 2 times, 80 DEG C of vacuum drying 12 hours, grinding, obtains manganous hydroxide powder;
5) by manganous hydroxide 1 gram, titanium gel 1 gram and ammonium molybdate 0.2 gram mixing, grinding 3 minutes, 600 DEG C of roastings 2 hours, grind 10 minutes, obtain acidic oxide MoO
3/ MnO
2/ TiO
2.
Described dispersant is glycerine.
embodiment 3
A kind of acidic oxide MoO
3/ MnO
2/ TiO
2preparation method comprise the following steps:
1) by dispersant 8 milliliters, deionized water 50 milliliters and Manganous sulfate monohydrate 1.5 grams mixing, room temperature lower magnetic force stirs 12 hours, obtains solution A;
2) 1.0 grams of NaOH are dissolved in deionized water, obtain solution B;
3) solution B is dropwise joined in solution A, stirring at room temperature 12 hours;
4) centrifugal, precipitate with deionized water supersound washing 2 times, then use absolute ethanol washing 2 times, 80 DEG C of vacuum drying 12 hours, grinding, obtains manganous hydroxide powder;
5) by manganous hydroxide 1 gram, titanium gel 1 gram and ammonium molybdate 0.2 gram mixing, grinding 3 minutes, 600 DEG C of roastings 2 hours, grind 10 minutes, obtain acidic oxide MoO
3/ MnO
2/ TiO
2.
Described dispersant is volume ratio is the ethylene glycol of 1:1 and the mixed liquor of glycerine.
Application examples 1
For the esterification of ethanol and acetic acid, in the three-neck flask of 150mL, add ethanol and acetic acid, its mol ratio is 3:1, catalyst (the acidic oxide MoO that embodiment 1 is obtained
3/ MnO
2/ TiO
2) consumption is 1% of reactant gross mass, with the electric jacket heating flask to 80 DEG C of band magnetic agitation, after magnetic agitation reaction 3h, conversion ratio reaches 60%, reuses 5 times, and catalytic effect is without obvious decline.
Application examples 2
For the esterification of ethanol and acetic acid, in the three-neck flask of 150mL, add ethanol and acetic acid, its mol ratio is 3:1, catalyst (the acidic oxide MoO that embodiment 2 is obtained
3/ MnO
2/ TiO
2) consumption is 5% of reactant gross mass, with the electric jacket heating flask to 95 DEG C of band magnetic agitation, after magnetic agitation reaction 6h, conversion ratio reaches 90%, reuses 5 times, and catalytic effect is without obvious decline.
Application examples 3
For the esterification of ethanol and acetic acid, in the three-neck flask of 150mL, add ethanol and acetic acid, its mol ratio is 3:1, catalyst (the acidic oxide MoO that embodiment 3 is obtained
3/ MnO
2/ TiO
2) consumption is 3% of reactant gross mass, with the electric jacket heating flask to 90 DEG C of band magnetic agitation, after magnetic agitation reaction 4h, conversion ratio reaches 80%, reuses 5 times, and catalytic effect is without obvious decline.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. an acidic oxide MoO
3/ MnO
2/ TiO
2preparation method, it is characterized in that: comprise the following steps:
By dispersant 5-10 milliliter, deionized water 40-60 milliliter and Manganous sulfate monohydrate 1.0-2.0 gram of mixing, room temperature lower magnetic force stirs 12 hours, obtains solution A;
0.7-1.3 gram of NaOH is dissolved in deionized water, obtains solution B;
Solution B is dropwise joined in solution A, stirring at room temperature 12 hours;
Centrifugal, precipitate with deionized water supersound washing 2 times, then use absolute ethanol washing 2 times, 80 DEG C of vacuum drying 12 hours, grinding, obtains manganous hydroxide powder;
By manganous hydroxide 1 gram, titanium gel 1 gram and ammonium molybdate 0.2 gram mixing, grinding 3 minutes, 600 DEG C of roastings 2 hours, grind 10 minutes, obtain acidic oxide MoO
3/ MnO
2/ TiO
2.
2. acidic oxide MoO according to claim 1
3/ MnO
2/ TiO
2preparation method, it is characterized in that: described dispersant is one or both in ethylene glycol, glycerine.
3. the acidic oxide MoO that the method for claim 1 is obtained
3/ MnO
2/ TiO
2.
4. the acidic oxide MoO that the method for claim 1 is obtained
3/ MnO
2/ TiO
2application, it is characterized in that: described acidic oxide MoO
3/ MnO
2/ TiO
2be applied to esterification and the ester exchange reaction of acid alcohol.
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| CN201510194685.2A CN104857951B (en) | 2015-04-23 | 2015-04-23 | A kind of acidic oxide MoO3/MnO2/TiO2Preparation method |
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|---|---|---|---|
| CN201510194685.2A CN104857951B (en) | 2015-04-23 | 2015-04-23 | A kind of acidic oxide MoO3/MnO2/TiO2Preparation method |
Publications (2)
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|---|---|
| CN104857951A true CN104857951A (en) | 2015-08-26 |
| CN104857951B CN104857951B (en) | 2017-12-08 |
Family
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Citations (6)
| 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 |
| 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 |
| 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 |
| CN103466712A (en) * | 2013-08-26 | 2013-12-25 | 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 |
-
2015
- 2015-04-23 CN CN201510194685.2A patent/CN104857951B/en active Active
Patent Citations (6)
| 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 |
| 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 |
| 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 |
| CN103466712A (en) * | 2013-08-26 | 2013-12-25 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| RUSIENE M. DE ALMEIDA,ET AL: "Improvements in acidity for TiO2 and SnO2 via impregnation with MoO3 for the esterification of fatty acids", 《CATALYSIS COMMUNICATIONS》 * |
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| CN104857951B (en) | 2017-12-08 |
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