CN106698417A - Method for preparing sulfur-free expansible graphite - Google Patents
Method for preparing sulfur-free expansible graphite Download PDFInfo
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- CN106698417A CN106698417A CN201510788840.3A CN201510788840A CN106698417A CN 106698417 A CN106698417 A CN 106698417A CN 201510788840 A CN201510788840 A CN 201510788840A CN 106698417 A CN106698417 A CN 106698417A
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- graphite
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Abstract
The invention belongs to the field of preparation of functional materials and discloses a method for preparing sulfur-free expansible graphite. The method comprises the following steps: (1) subjecting graphite to a contact reaction with acid so as to obtain a mixture; (2) carrying out a first expansion reaction on the mixture obtained in the step (1) so as to obtain first expansible graphite; and (3) carrying out a second expansion reaction on the first expansible graphite obtained in the step (2). By adopting the method disclosed by the invention, the sulfur-free expansible graphite which is free of sulfur and high in expanded ratio can be prepared; and the reaction is simple, the yield is high, the cost is low, no pollution is caused, and the operation is easy, so that large-scale production can be carried out.
Description
Technical field
The invention belongs to the preparation field of the composite on atom and molecule yardstick, i.e. belong to material technology
Field, the present invention relates to a kind of preparation method of expandable sulfur-free graphite, in particular it relates to one
Plant and graphite is reacted so as to prepare the novel processing step of expandable sulfur-free graphite with acid.
Background technology
Expansible graphite (Expansible Graphite) is compound on a kind of new atom and molecule yardstick
Material is presented unique physical and chemical performance, and expanded graphite is also a kind of wide excellent encapsulant
It is general to be applied to the industries such as oil, chemical industry, metallurgy, machinery, atomic energy, thermoelectricity, enjoy " sealing king "
Good reputation.
Due to it maintain the heat conduction of graphite, electric conductivity therefore electrode material, electromagnetic shielding, heat conduction,
Conductive, composite aspect is also widely used.
The method that tradition prepares expansible graphite is typically all using the concentrated sulfuric acid or concentrated nitric acid/potassium permanganate
Intercalator is done, and it is directly swollen at 700-900 DEG C by a series of links such as intercalation-washing-dryings
Change manufacture expansible graphite, the sulphur of its remaining when as encapsulant can corrode contacted sealing
Part, and oxidation resistance is poor.Environment temperature it is higher and with the presence of oxidant under conditions of easily by
Oxidation, makes sealing effectiveness reduction even fail.
Therefore, the problem of existing defects in the method for preparing expansible graphite in the prior art how is overcome,
A kind of new method for preparing expandable sulfur-free graphite is developed to need further to study.
The content of the invention
It is an object of the invention to provide a kind of preparation method of expandable sulfur-free graphite, the method is directed to existing
Have in the method that expansible graphite is prepared in technology and there is a problem of the high or low sulphur of sulfur content, propose a kind of
Graphite is reacted so as to prepare the novel processing step of expandable sulfur-free graphite with acid.
To achieve these goals, the present invention provides a kind of preparation method of expandable sulfur-free graphite, the party
Method is comprised the following steps：
(1) graphite and acid are carried out into haptoreaction, obtains mixture；
(2) mixture obtained through step (1) is carried out into the first expansion reaction, obtains first swollen
Swollen graphite；
(3) first expanded graphite obtained through step (2) is carried out into the second expansion reaction.
By above-mentioned technical proposal, the present invention is reacted by by graphite with acid, and by reexpansion,
So as to prepare expandable sulfur-free graphite, can be prepared without sulphur using the method for the present invention and expansion multiple is high
The expandable sulfur-free graphite of (can reach 800mL/g), and reaction is simple, yield high, low cost,
It is pollution-free, easily operated, can be mass produced.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Following specific embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is that the SEM figures of the sulphur-free expanded graphite that embodiments in accordance with the present invention 1 are prepared (are put
It is big 1000 times).
Fig. 2 is that the SEM figures of the sulphur-free expanded graphite that embodiments in accordance with the present invention 1 are prepared (are put
It is big 10000 times).
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of preparation method of expandable sulfur-free graphite, the method is comprised the following steps：
(1) graphite and acid are carried out into haptoreaction, obtains mixture；
(2) mixture obtained through step (1) is carried out into the first expansion reaction, obtains first swollen
Swollen graphite；
(3) first expanded graphite obtained through step (2) is carried out into the second expansion reaction.
Preferably, in the present invention, the graphite be natural scale graphite, and the graphite carbon content
It is preferred more than or equal to 99.6 weight % (i.e., >=99.6 weight %), and the particle mean size of the graphite
It is 100-350 mesh.
According to the present invention, the present inventor is had found by substantial amounts of scientific experiment, and graphite is entered with acid
Row contact, can prepare expandable sulfur-free graphite.
Preferably, in step (1), the acid is the one kind or many in perchloric acid, nitric acid and sulfuric acid
Kind.
It is particularly preferred that the acid is perchloric acid, and the concentration of the perchloric acid is 60-85 weight %；
More preferably 70-75 weight %.When especially, using the perchloric acid of concentration of the present invention, prepare
The expandable sulfur-free graphite yield for obtaining is high and best in quality.
According to the present invention, it is not particularly limited to graphite and acid are carried out into catalytic equipment, Ke Yiwei
The conventional selection of those skilled in the art, in the present invention, it is preferred to carry out in a kettle..
Preferably, in step (1), the graphite is 1 with the consumption weight ratio of the acid：0.1-1；
In the case of more preferably, the graphite is 1 with the consumption weight ratio of the acid：0.4-0.7.It is of the invention
The consumption metering of the acid is what is measured with the situation containing water, that is to say, that in above-mentioned amount ratio
Contain water in the consumption of acid.
According to the present invention, in step (1), graphite and acid are carried out into haptoreaction, it is preferable that institute
Stating catalytic condition includes：Temperature is 30-45 DEG C, and the time is 20-60 minutes；It is further preferred that
The catalytic condition includes：Temperature is 35-40 DEG C, and the time is 35-45 minutes.
According to the present invention, in step (2), the mixture obtained through step (1) is carried out
One expansion reaction；Preferably, the condition of first expansion reaction includes：Temperature is 200-400 DEG C,
Time is 15-60 minutes；It is further preferred that the condition of first expansion reaction includes：Temperature is
250-300 DEG C, the time is 30-45 minutes.
Preferably, first expansion reaction can be carried out in a kettle..
The present inventor is had found by substantial amounts of scientific experiment, preferably described in step (2)
First expansion reaction is carried out in the presence of protective gas, is so conducive to obtaining better quality, yield higher
And expandable sulfur-free graphite that expansion multiple is bigger.The protective gas can be including nitrogen, argon gas etc..
, according to the invention it is preferred to first expanded graphite obtained through step (2) is cooled to room temperature,
Then the second expansion reaction is carried out in the presence of a catalyst again.
Preferably, in step (3), second expansion reaction is carried out in the presence of a catalyst, institute
It is one or more in perchloric acid, nitric acid and sulfuric acid to state catalyst；It is further preferred that the catalyst
It is perchloric acid.
In the present invention, in step (3), the catalyst can be the acid in step (1),
That is, the catalyst in step (3) can be by not separating step (1) and step (2)
Reactant and obtain, or new catalyst of the present invention can also be added in the step (3).
Preferably, in step (3), the condition of second expansion reaction includes：Temperature is
600-800 DEG C, the time is 10-20s；In the case of more preferably, the condition bag of second expansion reaction
Include：Temperature is 650-700 DEG C, and the time is 12-15s.
Preferably, the graphite and the consumption weight ratio of the catalyst are 1：0.1-0.5；More preferably
The ground graphite is 1 with the consumption weight ratio of the catalyst：0.2-0.4.
According to the present invention, the equipment to first expansion reaction and second expansion reaction is no specific
Limit, can be the conventional selection of those skilled in the art, in the present invention, it is preferred to be carried out in beaker.
Below will the present invention will be described in detail by embodiment.
In case of no particular description, various materials used below are all from commercially available.
Present invention expansion multiple as described below passes through《GBT 10698-1989 expansible graphites》Method
Obtain.
The following expandable sulfur-free graphite for preparing of the invention is what the graphite flake layer spacing without sulphur expanded
The graphite of volumetric expansion.
Sulfur content of the invention is entered by sulphur meter (model is Thermo Flash 2000CHNS/O)
Row determines what is obtained.
Embodiment 1-11 is used to illustrate the preparation method of expandable sulfur-free graphite of the invention.
Embodiment 1
(1) by natural flake graphite (carbon content >=99.99 weight %) that particle mean size is 325 mesh with
Concentration is that the perchloric acid of 72 weight % is well mixed, and to put it into and carry out haptoreaction in reactor,
Wherein, natural flake graphite (common 15g) and the consumption weight ratio of perchloric acid are 1：0.5；And carry out
Catalytic condition includes：Reaction temperature is 38 DEG C, and the duration is 40min；
(2) mixture obtained through step (1) is carried out into the first expansion reaction under anaerobic,
The condition of first expansion reaction includes：Temperature is 280 DEG C, and the time is 40 minutes；
(3) it is added thereto to after first expanded graphite obtained through step (2) is cooled to room temperature
Catalyst DGG carries out the second expansion reaction；Relative to the graphite of 1 weight portion, the catalyst
Consumption be 0.3 weight portion, and the condition of second expansion reaction includes：Temperature is 680 DEG C,
Reaction time is 15s, obtains the expandable sulfur-free graphite that yield is 5.7%.
Expansion multiple measurement and chemical analysis are carried out after the expandable sulfur-free graphite is cooled to room temperature.
As a result：The sulfur content of prepared expandable sulfur-free graphite is 0, and expansion multiple is 800mL/g.
The SEM figures of the expandable sulfur-free graphite that the present embodiment is obtained such as Fig. 1 (amplifying 1000 times)
It is shown with Fig. 2 (amplifying 10000 times).
Embodiment 2
(1) by natural flake graphite (carbon content >=99.98 weight %) that particle mean size is 325 mesh with
Concentration is that the perchloric acid of 75 weight % is well mixed, and to put it into and carry out haptoreaction in reactor,
Wherein, natural flake graphite (common 15g) and the consumption weight ratio of perchloric acid are 1：0.7；And carry out
Catalytic condition includes：Reaction temperature is 40 DEG C, and the duration is 42min；
(2) mixture obtained through step (1) is carried out into the first expansion reaction under anaerobic,
The condition of first expansion reaction includes：Temperature is 300 DEG C, and the time is 44 minutes；
(3) it is added thereto to after first expanded graphite obtained through step (2) is cooled to room temperature
Catalyst DGG carries out the second expansion reaction；Relative to the graphite of 1 weight portion, the catalyst
Consumption be 0.2 weight portion, and the condition of second expansion reaction includes：Temperature is 660 DEG C,
Reaction time is 12s, obtains the expandable sulfur-free graphite that yield is 5.4%.
Expansion multiple measurement and chemical analysis are carried out after the expandable sulfur-free graphite is cooled to room temperature.
As a result：The sulfur content of prepared expandable sulfur-free graphite is 0, and expansion multiple is 796mL/g.
The SEM figures of the expandable sulfur-free graphite that the present embodiment is obtained are similar to embodiment 1 shown.
Embodiment 3
(1) by natural flake graphite (carbon content >=99.96 weight %) that particle mean size is 325 mesh with
Concentration is that the perchloric acid of 70 weight % is well mixed, and to put it into and carry out haptoreaction in reactor,
Wherein, natural flake graphite (common 15g) and the consumption weight ratio of perchloric acid are 1：0.4；And carry out
Catalytic condition includes：Reaction temperature is 35 DEG C, and the duration is 35min；
(2) mixture obtained through step (1) is carried out into the first expansion reaction under anaerobic,
The condition of first expansion reaction includes：Temperature is 250 DEG C, and the time is 32 minutes；
(3) it is added thereto to after first expanded graphite obtained through step (2) is cooled to room temperature
Catalyst DGG carries out the second expansion reaction；Relative to the graphite of 1 weight portion, the catalyst
Consumption be 0.4 weight portion, and the condition of second expansion reaction includes：Temperature is 690 DEG C,
Reaction time is 15s, obtains the expandable sulfur-free graphite that yield is 5.8%.
Expansion multiple measurement and chemical analysis are carried out after the expandable sulfur-free graphite is cooled to room temperature.
As a result：The sulfur content of prepared expandable sulfur-free graphite is 0, and expansion multiple is 800mL/g.
The SEM figures of the expandable sulfur-free graphite that the present embodiment is obtained are similar to embodiment 1 shown.
Embodiment 4
Expandable sulfur-free graphite is prepared according to method same as Example 1, except that, this implementation
The acid used in the step of example (1) is the nitric acid of 72 weight %.
Remaining is in the same manner as in Example 1.
As a result：The expandable sulfur-free graphite that yield is 4.6% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 756mL/g.
Embodiment 5
Expandable sulfur-free graphite is prepared according to method same as Example 3, except that, this implementation
The acid used in the step of example (1) is the perchloric acid of 82 weight %.
Remaining is in the same manner as in Example 3.
As a result：The expandable sulfur-free graphite that yield is 4.9% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 721mL/g.
Embodiment 6
Expandable sulfur-free graphite is prepared according to method same as Example 1, except that, this implementation
The graphite of example is 1 with the consumption weight ratio of the acid：1.
Remaining is in the same manner as in Example 1.
As a result：The expandable sulfur-free graphite that yield is 4.8% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 745mL/g.
Embodiment 7
Expandable sulfur-free graphite is prepared according to method same as Example 6, except that, this implementation
The graphite of example is 1 with the consumption weight ratio of the acid：0.2.
Remaining is in the same manner as in Example 6.
As a result：The expandable sulfur-free graphite that yield is 4.5% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 756mL/g.
Embodiment 8
Expandable sulfur-free graphite is prepared according to method same as Example 2, except that, this implementation
Example the step of (1) in catalytic condition be：Temperature is 45 DEG C.
Remaining is in the same manner as in Example 2.
As a result：The expandable sulfur-free graphite that yield is 4.6% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 768mL/g.
Embodiment 9
Expandable sulfur-free graphite is prepared according to method same as Example 2, except that, this implementation
Example the step of (1) in catalytic condition be：Temperature is 30 DEG C.
Remaining is in the same manner as in Example 2.
As a result：The expandable sulfur-free graphite that yield is 4.6% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 756mL/g.
Embodiment 10
Expandable sulfur-free graphite is prepared according to method same as Example 9, except that, this implementation
Example the step of (1) in catalytic condition be：Time is 45min.
Remaining is in the same manner as in Example 9.
As a result：The expandable sulfur-free graphite that yield is 4.6% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 758mL/g.
Embodiment 11
Expandable sulfur-free graphite is prepared according to method same as Example 3, except that, this implementation
The step of example (2), is carried out under aerobic conditions.
Remaining is in the same manner as in Example 3.
As a result：The expandable sulfur-free graphite that yield is 4.7% is obtained, and in the expandable sulfur-free graphite
Sulfur content is 0, and expansion multiple is 710mL/g.
Comparative example 1
This comparative example prepares expansible graphite according to method similar to Example 1, except that, this
Reexpansion is not used in comparative example and only with once expanding, specifically：
(1) by natural flake graphite (carbon content >=99.99 weight %) that particle mean size is 325 mesh with
Concentration is that the perchloric acid of 72 weight % is well mixed, and to put it into and carry out haptoreaction in reactor,
Wherein, natural flake graphite (common 15g) and the consumption weight ratio of perchloric acid are 1：0.5；And carry out
Catalytic condition includes：Reaction temperature is 38 DEG C, and the duration is 40min；
(2) mixture that will be obtained through step (1) exists in oxygen free condition and catalyst DGG
Under carry out the first expansion reaction, relative to the graphite of 1 weight portion, the consumption of the catalyst is 0.3
Weight portion, and the condition of first expansion reaction includes：Temperature is 680 DEG C, and the reaction time is 15s,
Obtain the expandable sulfur-free graphite that yield is 1.8%.
Expansion multiple measurement and chemical analysis are carried out after the expandable sulfur-free graphite is cooled to room temperature.
As a result：The sulfur content of prepared expandable sulfur-free graphite is 0, and expansion multiple is 109mL/g.
Be can be seen that by the result of above example and comparative example：Prepared using the method for the present invention
Expandable sulfur-free graphite have the advantages that high without sulphur, expansion multiple, highest can reach 800mL/g's
Advantage, and method of the present invention reaction is simple, low cost, it is pollution-free, easily operated, can carry out it is big
Large-scale production.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.Additionally need
It is bright, each particular technique feature described in above-mentioned specific embodiment, in reconcilable feelings
Under condition, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention
Various possible combinations are no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of expandable sulfur-free graphite, the method is comprised the following steps：
(1) graphite and acid are carried out into haptoreaction, obtains mixture；
(2) mixture obtained through step (1) is carried out into the first expansion reaction, obtains first swollen
Swollen graphite；
(3) first expanded graphite obtained through step (2) is carried out into the second expansion reaction.
2. method according to claim 1, wherein, in step (1), the carbon of the graphite
Content is more than or equal to 99.6 weight %, and particle mean size is 100-350 mesh.
3. method according to claim 1, wherein, in step (1), the acid is chlorine high
One or more in acid, nitric acid and sulfuric acid；Preferably
The acid is perchloric acid, and the concentration of the perchloric acid is 60-85 weight %.
4. the method according to any one in claim 1-3, wherein, the graphite with it is described
The consumption weight ratio of acid is 1：0.1-1, preferably 1：0.4-0.7.
5. method according to claim 1, wherein, in step (1), the haptoreaction
Condition include：Temperature is 30-45 DEG C, and the time is 20-60 minutes；Preferably
The catalytic condition includes：Temperature is 35-40 DEG C, and the time is 35-45 minutes.
6. method according to claim 1, wherein, in step (2), first expansion
The condition of reaction includes：Temperature is 200-400 DEG C, and the time is 15-60 minutes；Preferably
The condition of first expansion reaction includes：Temperature is 250-300 DEG C, and the time is 30-45 minutes.
7. the method according to claim 1 or 6, wherein, in step (2), described first
Expansion reaction is carried out in the presence of protective gas.
8. method according to claim 1, wherein, in step (3), second expansion
Reaction is carried out in the presence of a catalyst, and the catalyst is the one kind or many in perchloric acid, nitric acid and sulfuric acid
Kind；Preferably
The catalyst is perchloric acid.
9. method according to claim 1, wherein, in step (3), second expansion
The condition of reaction includes：Temperature is 600-800 DEG C, and the time is 10-20s；Preferably
The condition of second expansion reaction includes：Temperature is 650-700 DEG C, and the time is 12-15s.
10. method according to claim 8, wherein, the consumption of the graphite and the catalyst
Weight ratio is 1：0.1-0.5；Preferably
The graphite is 1 with the consumption weight ratio of the catalyst：0.2-0.4.
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| CN201510788840.3A CN106698417A (en) | 2015-11-17 | 2015-11-17 | Method for preparing sulfur-free expansible graphite |
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| CN201510788840.3A CN106698417A (en) | 2015-11-17 | 2015-11-17 | Method for preparing sulfur-free expansible graphite |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109574001A (en) * | 2019-01-09 | 2019-04-05 | 哈尔滨工业大学 | A kind of preparation method of the low temperature without sulphur, heavy metal free expansible graphite |
| CN110371969A (en) * | 2019-08-27 | 2019-10-25 | 哈尔滨市兴显卓科技有限公司 | A kind of smokeless preparation method of preparation method and sulphur-free expanded graphite without discharge expansible graphite |
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| CN101100298A (en) * | 2007-08-07 | 2008-01-09 | 哈尔滨工程大学 | Method for preparing expanded graphite |
| CN103539111A (en) * | 2013-11-05 | 2014-01-29 | 中国科学院山西煤炭化学研究所 | Preparation method of high thermal conductivity natural flexible graphite film |
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| CN101100298A (en) * | 2007-08-07 | 2008-01-09 | 哈尔滨工程大学 | Method for preparing expanded graphite |
| CN103539111A (en) * | 2013-11-05 | 2014-01-29 | 中国科学院山西煤炭化学研究所 | Preparation method of high thermal conductivity natural flexible graphite film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109574001A (en) * | 2019-01-09 | 2019-04-05 | 哈尔滨工业大学 | A kind of preparation method of the low temperature without sulphur, heavy metal free expansible graphite |
| CN109574001B (en) * | 2019-01-09 | 2021-11-30 | 哈尔滨工业大学 | Preparation method of low-temperature sulfur-free and heavy metal-free expandable graphite |
| CN110371969A (en) * | 2019-08-27 | 2019-10-25 | 哈尔滨市兴显卓科技有限公司 | A kind of smokeless preparation method of preparation method and sulphur-free expanded graphite without discharge expansible graphite |
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