CN102553571B - Preparation method of expandable graphite based composite material - Google Patents
Preparation method of expandable graphite based composite material Download PDFInfo
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- CN102553571B CN102553571B CN 201010578781 CN201010578781A CN102553571B CN 102553571 B CN102553571 B CN 102553571B CN 201010578781 CN201010578781 CN 201010578781 CN 201010578781 A CN201010578781 A CN 201010578781A CN 102553571 B CN102553571 B CN 102553571B
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Abstract
The invention discloses an expandable graphite based composite material, its preparation method and an application thereof. The composite material contains expandable graphite and Mn2O3 which is mixed with expandable graphite. The preparation method contains the following steps of: mixing ethanol and concentrated nitric acid to prepare a mixed solution; adding a manganese salt solution and flake graphite into the mixed solution to prepare a fluid suspension containing manganese ions; performing a hydrothermal reaction on the fluid suspension containing manganese ions at the temperature of 100-200 DEG C; cooling a product formed by the hydrothermal reaction, carrying out solid-liquid separation, and collecting a solid; and washing, drying, calcining and cooling the solid to obtain the expandable graphite based composite material. According to the preparation method of the expandable graphite based composite material, the expandable graphite based composite material is prepared by an expandable graphite and Mn2O3 one-step synthesis method. The method provided by the invention has advantages of simple technology, less amount of raw materials, little environmental pollution and low cost. Simultaneously, the expandable graphite based composite material has high catalysis efficiency.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, the concrete a kind of expanded graphite-based composite material and its preparation method and application that relates to.
Background technology
Energy-conservation and environmental protection is two problems of paying close attention to 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 in moment, need to add the effective catalyst of hydrogen peroxide decomposes.
Prepare Mn in the prior art
2O
3Method need through two steps, the first step is to add precipitating reagent earlier to generate hydroxide or carbonate deposition, and then through high-temperature calcination.This method complex process, power consumption is big, cost height, and the Mn that generates
2O
3Purity is not high.
The preparation method of expanded graphite-based composite material is by preparing expanded graphite earlier in the prior art, be that raw material reaction makes composite again with the expanded graphite, rather than directly be the direct synthetic expanded graphite-based composite material of a step of raw material with the native graphite, its complex process, troublesome poeration, and the raw material materials are big, environmental pollution is serious, the cost height.
Summary of the invention
The purpose of the embodiment of the invention is to overcome the above-mentioned deficiency of prior art, provides that a kind of pollution is little, cost is low, simple expanded graphite-based composite material of technology and preparation method thereof.
And, above-mentioned expanded graphite-based composite material in decomposition of hydrogen peroxide as Application of Catalyst.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of expanded graphite-based composite material, the Mn that comprises expanded graphite and mix mutually with expanded graphite
2O
3
And a kind of expanded graphite-based composite material preparation method comprises the steps:
Ethanol is mixed the preparation mixed solution with red fuming nitric acid (RFNA);
Add manganese salt solution and crystalline flake graphite in described mixed solution, preparation contains the suspension of manganese ion;
The described suspension that contains manganese ion is carried out hydro-thermal reaction under 100～200 ℃;
To carry out Separation of Solid and Liquid after the formed product cooling of described hydro-thermal reaction, and collect solid;
With described solids wash, drying, calcining, cooling obtains described expanded graphite-based composite material.
The present invention also provide above-mentioned expanded graphite-based composite material in decomposition of hydrogen peroxide as Application of Catalyst.
Expanded graphite-based composite material of the present invention comprises expanded graphite and the Mn of mutual doping
2O
3, making this expanded graphite-based composite material Stability Analysis of Structures, its preparation method adopts expanded graphite and Mn
2O
3One-step synthesis is prepared from, and this method technology is simple, and need not a large amount of strong acid and strong oxidizer, and environmental pollution is little, cost is low, in calcination process, and expanded graphite and Mn
2O
3Evenly mix, make this expanded graphite-based composite material Stability Analysis of Structures.When this composite is used for the catalyst of decomposing oxidation hydrogen, its catalytic efficiency height.
Description of drawings
Fig. 1 is expanded graphite-based composite material preparation method process flow diagram of the present invention.
Fig. 2 is the electron-microscope scanning figure of the expanded graphite-based composite material of the embodiment of the invention 1 preparation.
The specific embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The embodiment of the invention provides a kind of Stability Analysis of Structures, expanded graphite-based composite material that purity is high, the Mn that comprises expanded graphite and mix mutually with expanded graphite
2O
3This expanded graphite-based composite material is by expanded graphite and Mn
2O
3Mix mutually, make this expanded graphite-based composite material Stability Analysis of Structures.
Above-mentioned expanded graphite and Mn
2O
3Mass ratio be preferably 1: 1～10, more preferably 1: 2～5.
The embodiment of the invention provides also that a kind of pollution is little, cost is low, the simple expanded graphite-based composite material preparation method of technology, and as shown in Figure 1, this expanded graphite-based composite material is the preparation method comprise the steps:
S1: ethanol is mixed the preparation mixed solution with nitric acid;
S2: add manganese salt solution and crystalline flake graphite in described mixed solution, preparation contains the suspension of manganese ion;
S3: the described suspension that contains manganese ion is carried out hydro-thermal reaction under 100～200 ℃;
S4: will carry out Separation of Solid and Liquid after the formed product cooling of described hydro-thermal reaction, and collect solid;
S5: with described solids wash, drying, calcining, cooling obtains described expanded graphite-based composite material.
Like this, embodiment of the invention expanded graphite-based composite material preparation method adopts expanded graphite and Mn
2O
3One-step synthesis prepares expanded graphite-based composite material, and this method technology is simple, and need not a large amount of strong acid and strong oxidizer, and environmental pollution is little, cost is low.
Particularly, among above-mentioned expanded graphite-based composite material preparation method's the step S1, ethanol is preferably absolute ethyl alcohol, like this, can improve each component concentrations in the suspension of step S2 preparation, is convenient to improve the productive rate of expanded graphite-based composite material.The hydro-thermal reaction system that exists for of nitric acid provides a sour environment, plays the effect of crystalline flake graphite intercalation simultaneously and has avoided participating in of impurity.Wherein, nitric acid is preferably red fuming nitric acid (RFNA).The volume ratio of ethanol and red fuming nitric acid (RFNA) is preferably 60: 1～and 10.These both volume ratio scopes can better provide the environment of a hydro-thermal reaction.
Particularly, among above-mentioned expanded graphite-based composite material preparation method's the step S2, manganese salt is preferably at least a in manganese nitrate, manganese carbonate, manganese sulfate, manganese chloride, the manganese acetate.Manganese salt solution concentration is not particularly limited, and can when the expanded graphite-based composite material throughput requirements is big, can prepare the bigger manganese salt solution of mass concentration, as the 50wt% manganese nitrate solution according to the configuration of expanded graphite-based composite material demand.Mix in order to reduce impurity, this manganese salt is preferably analytically pure manganese salt.Certainly, when the configuration manganese salt solution, form uniform solution in order to make manganese salt, can add an amount of acid, for example, when the preparation manganese carbonate, can add an amount of acid and make it dissolving.This acid is preferably hydrochloric acid or nitric acid, to reduce participating in of impurity, to improve the purity of expanded graphite-based composite material.
Among this step S2, the manganese salt in the manganese salt solution and the mass ratio of crystalline flake graphite do not have special requirement, still, should satisfy both quality all greater than 0, be that both must exist simultaneously, preferably both additions should satisfy in expanded graphite-based composite material, expanded graphite and Mn
2O
3Mass ratio be preferably 1: 1～10, more preferably 1: 2～5.
Particularly, among above-mentioned expanded graphite-based composite material preparation method's the step S3, hydro-thermal reaction is to be to carry out under 100～200 ℃ in temperature, and this temperature has guaranteed Mn
2O
3Generation.Further, the temperature of hydro-thermal reaction is preferably 150～180 ℃, and more preferably 170 ℃, this preferred temperature range more is conducive to hydro-thermal reaction to generating Mn
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, 8～10h more preferably, and 12h more preferably, this preferred hydro-thermal reaction time can guarantee that more hydro-thermal reaction is complete, further saves unnecessary energy consumption.
The container of above-mentioned hydro-thermal reaction is preferably hydrothermal reaction kettle, because this hydrothermal reaction kettle when above-mentioned hydrothermal temperature is provided, can also provide rational air pressure, thereby is conducive to Mn
2O
3Generation.
In this step S3, crystalline flake graphite is oxidized and intercalation in hydrothermal reaction process.
Particularly, among above-mentioned expanded graphite-based composite material preparation method's the step S4, the type of cooling adopts this area mode commonly used to get final product, and in order to reduce operation, cuts down the consumption of energy, and preferably takes the mode of nature cooling.The mode that the product that hydro-thermal reaction is formed carries out Separation of Solid and Liquid can be to filter or the mode of collecting solid that can realize such as centrifugal all can.
Particularly, among above-mentioned expanded graphite-based composite material preparation method's the step S5, washing is in order to remove the impurity in the Separation of Solid and Liquid gained solid, as impurity such as ions, to reach the purpose of this solid of purifying.Mode to this solids wash is preferably this solid earlier with the distilled water washing, washs with ethanol then.This preferred washing scheme more is conducive to remove the impurity of sneaking in this solid, for example accessory substance that generates in above-mentioned hydro-thermal reaction.This washing scheme further is preferably after the cleaning solution pH value that adopts distilled water to wash this solid is 6～7, washs with ethanol again.Like this, more be conducive to remove the impurity that is mixed in this solid.
Among this step S5, be impurity and the moisture that remains in solid for further removing to the solid drying after the washing, make impurity and moisture volatilize in the process of heating, reached the purpose that is further purified solid.This drying mode is preferably the solid after the washing is preferably 50～100 ℃ in temperature, and the time is preferably 1～6h.Further preferred 50～60 ℃, the time is dry under the vacuum condition of 1～2h.
Among this step S5, be inflated in calcination process by the crystalline flake graphite behind the intercalation, and the Mn that generates with hydro-thermal reaction
2O
3Mix mutually, in cooling procedure, form stable expanded graphite-based Mn
2O
3Composite crystal.Thereby acquisition expanded graphite-based composite material.The temperature of this calcining is preferably 600 ℃, and the time of calcining is preferably 2h.This preferred calcining heat and time more are conducive to expanded graphite-based Mn
2O
3The formation of composite crystal is with stable.
The embodiment of the invention also provides the catalyst of above-mentioned expanded graphite-based composite material as decomposition of hydrogen peroxide.The embodiment of the invention is found after deliberation, in the decomposition of hydrogen peroxide process, adds above-mentioned expanded graphite-based composite material, can improve the speed of hydrogen peroxide decomposes effectively, thereby at abrupt release multipotency more.Can learn that thus expanded graphite-based composite material is the good catalyst of decomposition of hydrogen peroxide.
Now in conjunction with instantiation, the present invention is further elaborated.
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 3ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 3ml manganese nitrate solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 1.0g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 170 ℃, hydro-thermal reaction 12h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 6, uses absolute ethanol washing at last 2 times;
(6) under 60 ℃ of baking temperatures in vacuum drying chamber dry 2h;
(7) dried precipitation is transferred in the crucible, under 600 ℃ of calcining heats, is incubated 2h, obtain expanded graphite-based composite material.
As seen from Figure 2, edge and the inwall at expanded graphite has a large amount of Mn
2O
3Particle, these particle majorities are distributed in the edge of expanded graphite layer, are distributed on a small quantity in the expanded graphite hole, have certain agglomeration.
Embodiment 2
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 1ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 10ml manganese nitrate solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 2.0g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 200 ℃, hydro-thermal reaction 18h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 7, uses absolute ethanol washing at last 2 times;
(6) under 50 ℃ of baking temperatures in vacuum drying chamber dry 5h;
(7) dried precipitation is transferred in the crucible, under 550 ℃ of calcining heats, is incubated 4h, obtain expanded graphite-based composite material.
Embodiment 3
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 2ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 8ml manganese acetate solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 1.5g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 180 ℃, hydro-thermal reaction 10h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 6, uses absolute ethanol washing at last 2 times;
(6) under 70 ℃ of baking temperatures in vacuum drying chamber dry 3h;
(7) dried precipitation is transferred in the crucible, under 600 ℃ of calcining heats, is incubated 3h, obtain expanded graphite-based composite material.
Embodiment 4
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 4ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 5ml manganese sulfate solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 1.2g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 150 ℃, hydro-thermal reaction 6h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 6, uses absolute ethanol washing at last 2 times;
(6) under 80 ℃ of baking temperatures in vacuum drying chamber dry 4h;
(7) dried precipitation is transferred in the crucible, under 600 ℃ of calcining heats, is incubated 4h, obtain expanded graphite-based composite material.
Embodiment 5
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 5ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 2ml manganese carbonate solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 0.8g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 120 ℃, hydro-thermal reaction 16h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 7, uses absolute ethanol washing at last 2 times;
(6) under 90 ℃ of baking temperatures in vacuum drying chamber dry 2h;
(7) dried precipitation is transferred in the crucible, under 500 ℃ of calcining heats, is incubated 5h, obtain expanded graphite-based composite material.
Embodiment 6
The preparation method of the expanded graphite-based composite material of present embodiment comprises the steps:
(1) gets the mixed solution that 60ml absolute ethyl alcohol and 10ml concentrated nitric acid solution (mass fraction is 67%, and commercially available analysis is pure) are prepared the ethanol red fuming nitric acid (RFNA);
(2) 1ml manganese chloride solution (mass concentration 50%, commercially available analysis is pure) is dispersed in the above-mentioned mixed solution, forms manganese salt solution;
(3) the 1.0g natural flake graphite is scattered in the above-mentioned manganese salt solution, forms finely dispersed suspension;
(4) above-mentioned suspension is changed in the hydrothermal reaction kettle, under 170 ℃, hydro-thermal reaction 12h;
(5) naturally cool to room temperature, filter to isolate precipitation, being washed with distilled water to the filtrate pH value is 7, uses absolute ethanol washing at last 2 times;
(6) under 60 ℃ of baking temperatures in vacuum drying chamber dry 2h;
(7) dried precipitation is transferred in the crucible, under 600 ℃ of calcining heats, is incubated 2h, obtain expanded graphite-based composite material.
Expanded graphite-based composite material is as catalysis H
2O
2The application of decomposing
The catalytic activity of the expanded graphite-based composite material H of catalyst catalysis 1% under 15 ℃ alkali condition of unit mass
2O
2The decomposition reaction speed constant is measured.Get the H of 10ml 1% at every turn
2O
2, join 50ml 1molL
-1KOH solution in, the control reaction temperature is 15 ℃, adds the 20mg expanded graphite-based composite material under the magnetic agitation condition, records the O that different t constantly emit
2Volume V
tAnd the O that emits when decomposing fully
2Volume V
∞With ln (V
∞-V
t)/[V
t] to the t mapping, obtain a straight line, can obtain the reaction rate coefficient k from the slope of straight line.The catalytic activity of each embodiment gained expanded graphite-based composite material is listed in table 1.
The catalytic activity of the expanded graphite-based composite material of table 1. embodiment 1 to 6 preparation
As shown in Table 1, the prepared expanded graphite-based composite material decomposing H of embodiment of the invention expanded graphite-based composite material preparation method
2O
2In the catalytic activity height, wherein, the expanded graphite-based composite material of embodiment 1 preparation makes H
2O
2Decomposition rate constant is up to 0.73, this Mn
2O
3Composite efficient is also up to 0.61.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. an expanded graphite-based composite material preparation method comprises the steps:
Absolute ethyl alcohol is mixed the preparation mixed solution with red fuming nitric acid (RFNA); Wherein, the volume ratio of described absolute ethyl alcohol and red fuming nitric acid (RFNA) is 60:1～10;
Add manganese salt solution and crystalline flake graphite in described mixed solution, preparation contains the suspension of manganese ion;
The described suspension that contains manganese ion is carried out hydro-thermal reaction under 100～200 ℃;
To carry out Separation of Solid and Liquid after the formed product cooling of described hydro-thermal reaction, and collect solid;
With described solids wash, drying, calcining, cooling obtains described expanded graphite-based composite material.
2. expanded graphite-based composite material preparation method according to claim 1, it is characterized in that: the temperature of described hydro-thermal reaction is 150～180 ℃, the time is 1～5h.
3. expanded graphite-based composite material preparation method according to claim 1 and 2, it is characterized in that: the temperature of described hydro-thermal reaction is 170 ℃.
4. expanded graphite-based composite material preparation method according to claim 1 is characterized in that: the manganese salt in the described manganese salt solution is at least a in manganese nitrate, manganese carbonate, manganese sulfate, manganese chloride, the manganese acetate.
5. expanded graphite-based composite material preparation method according to claim 1, it is characterized in that: the drying of described solid is at 50～60 ℃ of following vacuum drying 1～12h with described solid.
6. expanded graphite-based composite material preparation method according to claim 1, it is characterized in that: the temperature of described calcining is 500～650 ℃, the time is 1～5h.
7. expanded graphite-based composite material preparation method according to claim 1 is characterized in that: the Mn that the composite of described method preparation comprises expanded graphite and mixes mutually with expanded graphite
2O
3
8. expanded graphite-based composite material preparation method according to claim 7 is characterized in that: the expanded graphite in the described expanded graphite-based composite material and Mn
2O
3Mass ratio be 1:1～10.
9. according to claim 7 or 8 described expanded graphite-based composite material preparation methods, it is characterized in that: described expanded graphite and Mn
2O
3Mass ratio be 1:2～5.
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| CN104261395A (en) * | 2014-09-28 | 2015-01-07 | 无锡市新颖密封材料厂 | Preparation method of expanded graphite-based composite material |
| CN104495834A (en) * | 2015-01-16 | 2015-04-08 | 黑龙江科技大学 | Method for preparing expandable graphite by replacing solid and liquid oxidizing agents with gaseous oxidizing agents |
| CN110551324A (en) * | 2019-09-26 | 2019-12-10 | 山东一诺威新材料有限公司 | Preparation method and application of nanoscale transition metal oxide loaded expanded graphite particles |
| CN110773151B (en) * | 2019-11-05 | 2022-04-01 | 吉林大学 | Porous bixbyite Mn loaded with diatomite2O3Catalyst, preparation method and application thereof |
| CN111689493B (en) * | 2020-07-03 | 2021-11-26 | 郑州中科新兴产业技术研究院 | Preparation method of expanded graphite cerium oxide or graphene cerium oxide composite material |
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| CN1768932A (en) * | 2005-10-24 | 2006-05-10 | 南开大学 | Expanded graphite supporting NiB amorphous alloy catalyst, its preparation method and application |
| CN101060038A (en) * | 2007-04-20 | 2007-10-24 | 哈尔滨工程大学 | Expanded graphite/metal oxide composite material and preparation method thereof |
| CN101521119A (en) * | 2007-04-20 | 2009-09-02 | 哈尔滨工程大学 | Preparation method of expanded graphite/metal oxide composite material |
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| CN1768932A (en) * | 2005-10-24 | 2006-05-10 | 南开大学 | Expanded graphite supporting NiB amorphous alloy catalyst, its preparation method and application |
| CN101060038A (en) * | 2007-04-20 | 2007-10-24 | 哈尔滨工程大学 | Expanded graphite/metal oxide composite material and preparation method thereof |
| CN101521119A (en) * | 2007-04-20 | 2009-09-02 | 哈尔滨工程大学 | Preparation method of expanded graphite/metal oxide composite material |
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