CN102557143B - Preparation method of Mn2O3 and catalyst - Google Patents

Preparation method of Mn2O3 and catalyst Download PDF

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Publication number
CN102557143B
CN102557143B CN201010576793.3A CN201010576793A CN102557143B CN 102557143 B CN102557143 B CN 102557143B CN 201010576793 A CN201010576793 A CN 201010576793A CN 102557143 B CN102557143 B CN 102557143B
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preparation
precipitation
mn2o3
hydro
manganese salt
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CN102557143A (en
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周明杰
邓惠仁
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention discloses a preparation method of Mn2O3, comprising the steps of mixing manganese salt solution and ethanol, performing a hydro-thermal reaction at 100-150 DEG C to generate Mn2O3 deposition; after cooling the product formed by the hydro-thermal reaction, separating solid and solution, and collecting the Mn2O3 deposition; washing and drying the Mn2O3 deposition to obtain the Mn2O3. In the invention, the preparation method of Mn2O3 only needs to directly mix the manganese solution and ethanol to generate Mn2O3, so that the method has a simple process, does not need high-temperature calcining, has less energy consumption, low cost and high purity; meanwhile, the method does not introduce other non-volatile ions, so that the purity of the prepared Mn2O3 is high. The Mn2O3 can be used as a catalyst for decomposing hydrogen oxide.

Description

A kind of Mn 2o 3preparation method and catalyzer
Technical field
The invention belongs to technical field of inorganic chemical industry, particularly relate to a kind of Mn 2o 3preparation method and catalyzer.
Background technology
Energy saving standard is two issues that need special attention of the world today, and therefore, efficient, novel, green environmentally friendly machine has become one of emphasis direction of various countries scientist research.Hydrogen peroxide is a kind of green high-capacity fuel, can be used in field of aerospace.In order to obtain high-energy instantaneously, needing the effective catalyst adding peroxide decomposition.
Mn is prepared in prior art 2o 3method need through two steps, the first step first adds precipitation agent to generate oxyhydroxide or carbonate deposition, and then through high-temperature calcination.The method complex process, power consumption is large, and cost is high, and the Mn generated 2o 3purity is not high.
Summary of the invention
The object of the embodiment of the present invention is the above-mentioned deficiency overcoming prior art, and provide a kind of less energy consumption, cost is low, the simple Mn of technique 2o 3preparation method.
And, above-mentioned Mn 2o 3mn prepared by preparation method 2o 3as the catalyzer of decomposition of hydrogen peroxide.
To achieve these goals, the technical scheme of the embodiment of the present invention is as follows:
A kind of Mn 2o 3preparation method, comprises the steps:
Manganese salt solution is mixed with ethanol, and carry out hydro-thermal reaction at 100 ~ 150 DEG C, generate Mn 2o 3precipitation;
Carry out solid-liquid separation after the product cooling described hydro-thermal reaction formed, and collect Mn 2o 3precipitation;
By Mn 2o 3washing of precipitate, dry, obtain described Mn 2o 3.
And, by above-mentioned Mn 2o 3mn prepared by preparation method 2o 3the application of catalyzer is done in decomposition of hydrogen peroxide.
Above-mentioned Mn 2o 3manganese salt solution and the direct hybrid reaction of ethanol only need can be generated Mn by preparation method 2o 3, the method technique is simple, and without the need to through high-temperature calcination, power consumption is few, and cost is low; Meanwhile, the method does not introduce other difficult volatility ion, the Mn of preparation 2o 3purity high.This Mn 2o 3when being used as the catalyzer decomposing hydrogen oxide, its catalytic efficiency is high.
Accompanying drawing explanation
Fig. 1 is the Mn of the embodiment of the present invention 2o 3preparation method's process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of less energy consumption, cost is low, the simple Mn of technique 2o 3preparation method, as shown in Figure 1, this Mn 2o 3preparation method comprises the steps:
S1: manganese salt solution is mixed with ethanol, and hydro-thermal reaction is carried out at 100 ~ 150 DEG C, generate Mn 2o 3precipitation;
S2: carry out solid-liquid separation after the product cooling described hydro-thermal reaction formed, and collect Mn 2o 3precipitation;
S3: by Mn 2o 3washing of precipitate, dry, obtain described Mn 2o 3.
Like this, embodiment of the present invention Mn 2o 3manganese salt solution and the direct hybrid reaction of ethanol can be generated Mn by preparation method 2o 3, the method technique is simple, and without the need to through high-temperature calcination, power consumption is few, and cost is low, is applicable to suitability for industrialized production; Meanwhile, the method does not introduce other difficult volatility ion, the Mn of preparation 2o 3purity high.
Particularly, above-mentioned Mn 2o 3in the step S1 of preparation method, manganese salt is preferably at least one in manganous nitrate, manganous carbonate, manganous sulfate, Manganous chloride tetrahydrate, manganous acetate.Manganese salt solution concentration is not particularly limited, can according to Mn 2o 3the output flexible configuration of demand, Mn 2o 3when throughput requirements is large, the manganese salt solution that mass concentration is larger can be prepared, as 50wt% manganese nitrate solution.Mix to reduce impurity, this manganese salt is preferably analytically pure manganese salt.Certainly, when configuring manganese salt solution, in order to the uniform solution of manganese salt formation can be made, appropriate acid can be added, such as, when preparing manganous carbonate, appropriate acid can be added and make it to dissolve.This acid is preferably a volatile acid, and example hydrochloric acid or nitric acid, to reduce participating in of impurity, to improve Mn 2o 3purity.Ethanol is preferably dehydrated alcohol, and like this, in lower step S2 after both mixing, the concentration of raising manganese salt that just can be relative and ethanol, is convenient to raising Mn 2o 3productive rate.
Particularly, above-mentioned Mn 2o 3in the step S2 of preparation method, the manganese salt in manganese salt solution mixes with ethanol and is preferably greater than 0 by the mass ratio of the manganese salt in manganese salt solution and ethanol, is less than or equal to the ratio mixing of 1/5.This blending ratio, is conducive to economizing in raw materials, and improves Mn 2o 3productive rate.
In this step S2, hydro-thermal reaction is carried out at temperature is 150 ~ 200 DEG C, and this temperature ensure that Mn 2o 3generation.Further, the temperature of hydro-thermal reaction is preferably 170 ~ 180 DEG C, more elects 180 DEG C as, and the reaction that this preferred temperature range is more conducive to manganese salt and ethanol is carried out namely to generating Mn to forward 2o 3the direction of product is carried out.Under the prerequisite of aforesaid hydrothermal temperature scope, the time of hydro-thermal reaction is preferably 6 ~ 24h, more preferably 8 ~ 10h, more elects 8h as, and this preferred time can ensure manganese salt and ethanol synthesis completely, and can save unnecessary energy consumption.
The container of above-mentioned hydro-thermal reaction is preferably hydrothermal reaction kettle, because this hydrothermal reaction kettle is while providing above-mentioned hydrothermal temperature, can also provides rational air pressure, thus be conducive to Mn 2o 3generation.
Particularly, above-mentioned Mn 2o 3in the step S3 of preparation method, the mode that the type of cooling adopts this area conventional, in order to reduce operation, reducing energy consumption, preferably taking the mode of naturally cooling.The mode that the product formed hydro-thermal reaction carries out solid-liquid separation can be filter or centrifugal etc. can realize collecting Mn 2o 3the mode of precipitation.
Particularly, above-mentioned Mn 2o 3in the step S4 of preparation method, washing is to remove Mn 2o 3impurity in precipitation, as ion etc., to reach purifying Mn 2o 3the object of precipitation.To Mn 2o 3the mode of washing of precipitate is preferably Mn 2o 3precipitation first uses distilled water wash, then uses washing with alcohol.This scheme of preferably washing more is conducive to removing Mn 2o 3the impurity be mixed in precipitation, the impurity of the by product such as generated in above-mentioned hydro-thermal reaction.This washing scheme is further preferably when adopting distilled water wash Mn 2o 3the washings pH value of precipitation is after 6 ~ 7, then uses washing with alcohol.Like this, be more conducive to removing and be mixed in Mn 2o 3the impurity of precipitation.
In this step S4, to the Mn after washing 2o 3it is for removing remains in Mn further that precipitation carries out drying 2o 3the impurity of precipitation and moisture, make impurity and moisture in the process volatilization of heating, reached and be further purified Mn 2o 3the object of precipitation.This drying mode is preferably the Mn after by washing 2o 3being deposited in temperature is 50 ~ 100 DEG C, is more preferably 60 ~ 80 DEG C, and the time is dry under the vacuum condition of 4 ~ 48h.Preferred selection vacuum-drying, is conducive to Mn 2o 3stablizing of product.Certainly, other conventional drying modes of this area are adopted also can to achieve the goal.
The embodiment of the present invention additionally provides above-mentioned Mn 2o 3mn prepared by preparation method 2o 3the catalyzer of action breaks hydrogen peroxide.Find after deliberation, in decomposition of hydrogen peroxide process, add above-mentioned Mn 2o 3mn prepared by preparation method 2o 3, effectively can improve the speed of peroxide decomposition, thus in abrupt release more multi-energy.Can learn thus, Mn prepared by the embodiment of the present invention 2o 3purity high, be the excellent catalyzer of decomposition of hydrogen peroxide.Its catalytic efficiency is high, sees shown in following table 1.
Now in conjunction with specific examples, the present invention is further elaborated.
Embodiment 1
Mn 2o 3preparation method, comprise the steps:
S11: 4ml manganese nitrate solution (mass concentration 50%, commercially available analytical pure) is dispersed in 56ml dehydrated alcohol, is mixed with mixing solutions;
S12: above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 180 DEG C of temperature, hydro-thermal reaction 8h;
S13: naturally cool to room temperature, filters to isolate precipitation, and being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
S14: under 80 DEG C of drying temperatures in vacuum drying oven dry 12h, obtain Mn 2o 3.
Embodiment 2
Mn 2o 3preparation method, comprise the steps:
(1) 3ml manganese nitrate solution (mass concentration 50%, commercially available analytical pure) is dispersed in 57ml dehydrated alcohol, is mixed with mixing solutions;
(2) above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 150 DEG C of temperature, hydro-thermal reaction 24h;
(3) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
(4) under 100 DEG C of drying temperatures in vacuum drying oven dry 4h, obtain Mn 2o 3.
Embodiment 3
Catalyzing hydrogen peroxide Mn 2o 3preparation method, comprise the steps:
(1) 5ml manganese nitrate solution (mass concentration 50%, commercially available analytical pure) is dispersed in 60ml dehydrated alcohol, is mixed with mixing solutions;
(2) above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 160 DEG C of temperature, hydro-thermal reaction 16h;
(3) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
(4) under 90 DEG C of drying temperatures in vacuum drying oven dry 6h, obtain catalyzing hydrogen peroxide Mn 2o 3.
Embodiment 4
Mn 2o 3preparation method, comprise the steps:
(1) 2ml manganese nitrate solution (mass concentration 50%, commercially available analytical pure) is dispersed in 60ml dehydrated alcohol, is mixed with mixing solutions;
(2) above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 170 DEG C of temperature, hydro-thermal reaction 10h;
(3) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
(4) under 70 DEG C of drying temperatures in vacuum drying oven dry 10h, obtain Mn 2o 3.
Embodiment 5
Mn 2o 3preparation method, comprise the steps:
(1) 2mg manganous carbonate is mixed with water, and to add volumetric concentration be 10% hydrochloric acid, be mixed with the manganous carbonate solution of 50%, this manganous carbonate solution mixed with 55ml dehydrated alcohol, is mixed with mixing solutions;
(2) above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 190 DEG C of temperature, hydro-thermal reaction 9h;
(3) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
(4) under 60 DEG C of drying temperatures in vacuum drying oven dry 24h, obtain Mn 2o 3.
Embodiment 6
Mn 2o 3preparation method, comprise the steps:
(1) be to mix at 1: 5 in mass ratio by Manganous chloride tetrahydrate and ethanol, be mixed with mixing solutions;
(2) above-mentioned mixing solutions is proceeded in hydrothermal reaction kettle, at 200 DEG C of temperature, hydro-thermal reaction 6h;
(3) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to filtrate pH value is 6 ~ 7, finally uses absolute ethanol washing 2 times;
(4) under 50 DEG C of drying temperatures in vacuum drying oven dry 48h, obtain Mn 2o 3.
Application examples 7
The H of catalyzer catalysis 1% under the alkaline condition of 15 DEG C of the catalytic activity unit mass of product 2o 2decomposition reaction rate constant measures.Get the H of 10ml 1% at every turn 2o 2, join 50ml 1molL -1kOH solution in, control temperature of reaction be 15 DEG C, under magnetic agitation condition, add 20mg catalyzing hydrogen peroxide Mn 2o 3, record not the O that t in the same time releases 2volume V tand the O released when decomposing completely 2volume V ∞.With ln (V ∞-V t)/[V t] to t mapping, obtain a straight line, reaction velocity coefficient k can be obtained from the slope of straight line.Each embodiment gained catalyzing hydrogen peroxide Mn 2o 3catalytic activity list in table 1.
Mn prepared by table 1 embodiment 1 ~ 6 2o 3in decomposing H 2o 2in catalytic activity
As shown in Table 1, embodiment of the present invention Mn 2o 3mn prepared by preparation method 2o 3decomposing H 2o 2in catalytic activity high, wherein, embodiment 1 prepare Mn 2o 3make H 2o 2decomposition rate constant up to 0.73, this Mn 2o 3catalytic efficiency is also up to 0.61.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. a Mn 2o 3preparation method, comprises the steps:
Manganese salt solution is mixed with ethanol, and carry out hydro-thermal reaction at 150 ~ 200 DEG C, generate Mn 2o 3precipitation; Described manganese salt is at least one in manganous carbonate, manganous sulfate, Manganous chloride tetrahydrate, manganous acetate, and also adds have appropriate acid when preparing described manganese salt solution;
Carry out solid-liquid separation after the product cooling described hydro-thermal reaction formed, and collect Mn 2o 3precipitation;
By Mn 2o 3washing of precipitate, dry, obtain described Mn 2o 3.
2. Mn according to claim 1 2o 3preparation method, is characterized in that: the temperature of described hydro-thermal reaction is 170 ~ 180 DEG C, and the time is 6 ~ 24h.
3. Mn according to claim 1 and 2 2o 3preparation method, is characterized in that: the temperature of described hydro-thermal reaction is 180 DEG C, and the time is 8 ~ 10h.
4. Mn according to claim 1 2o 3preparation method, is characterized in that: the manganese salt in described manganese salt solution and the mass ratio of ethanol are greater than 0, are less than or equal to 1/5.
5. Mn according to claim 1 2o 3preparation method, is characterized in that: described Mn 2o 3washing of precipitate is by Mn 2o 3precipitation first uses distilled water wash, then uses washing with alcohol.
6. Mn according to claim 5 2o 3preparation method, is characterized in that: described distilled water wash Mn 2o 3the washings pH value of precipitation is after 6 ~ 7, then uses washing with alcohol.
7. Mn according to claim 1 2o 3preparation method, is characterized in that: described Mn 2o 3the drying of precipitation is by described Mn 2o 3precipitation is dry under vacuum.
8. the Mn according to claim 1 or 6 2o 3preparation method, is characterized in that: described Mn 2o 3the temperature of the drying of precipitation is 50 ~ 100 DEG C, and the time is 4 ~ 48h.
CN201010576793.3A 2010-12-07 2010-12-07 Preparation method of Mn2O3 and catalyst Expired - Fee Related CN102557143B (en)

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CN103420426B (en) * 2013-08-29 2015-01-07 重庆工商大学 Method for pyrogenic decomposing manganous nitrate to generate Mn2O3
CN106140149B (en) * 2015-04-18 2019-03-22 中国石油化工股份有限公司 A kind of catalyst and a kind of method of peroxynitrite decomposition hydrogen
CN106140148B (en) * 2015-04-18 2019-03-22 中国石油化工股份有限公司 A kind of catalyst and a kind of method of peroxynitrite decomposition hydrogen
CN105967239B (en) * 2015-12-29 2017-12-15 内江师范学院 A kind of porous Cubic Mn2O3Submicron powder and preparation method thereof
CN106395908B (en) * 2016-09-06 2017-08-25 上海应用技术大学 A kind of bamboo joint structure Mn2O3Preparation method
CN106887606B (en) * 2017-02-23 2019-12-13 广西大学 Peach-shaped Mn2O3preparation method of/C particles
CN110773151B (en) * 2019-11-05 2022-04-01 吉林大学 Porous bixbyite Mn loaded with diatomite2O3Catalyst, preparation method and application thereof
CN115197542A (en) * 2021-04-12 2022-10-18 陆平林 Preparation method of high-melt-index degradable material
CN115025772A (en) * 2022-07-18 2022-09-09 西安交通大学 Supported vanadium-titanium synergistic denitration and demercuration catalyst and preparation method thereof

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