CN106219526A - A kind of method of purification of micro crystal graphite - Google Patents
A kind of method of purification of micro crystal graphite Download PDFInfo
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- CN106219526A CN106219526A CN201610568679.3A CN201610568679A CN106219526A CN 106219526 A CN106219526 A CN 106219526A CN 201610568679 A CN201610568679 A CN 201610568679A CN 106219526 A CN106219526 A CN 106219526A
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- micro crystal
- crystal graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses the method for purification of a kind of micro crystal graphite, the method is to be placed in high-pressure reactor by micro crystal graphite, it is sufficiently stirred for, airtight, adjust temperature and pressure, purification gas is made to enter supercriticality, leaching 20～90min in the reactor, it is cooled to room temperature, pressure release is to atmospheric pressure, it is then peeled off micro crystal graphite and waste liquid, washing, dry and i.e. can get high-purity micro crystal graphite, micro crystal graphite fixed carbon content after final purification may be up to more than 99.99, iron content is less than 10ppm, this method of purification is simple to operate, purify gas can recycle, with low cost, there is considerable application prospect.
Description
Technical field
The present invention relates to graphite purification field, be specifically related to the method for purification of a kind of micro crystal graphite.
Background technology
Natural micro crystal graphite is a kind of mineral products of China's rich reserves, and its granule is by the small crystalline substance of many random orientations
Body gathering forms, in isotropism.Its reserves are more than 200,000,000 t, and fixed carbon content is mostly 75% ~ 90%, industrial the most direct
Using high-grade raw ore, with low content of technology, mostly with thick production and sale, resource is not fully utilized, and causes resource
Serious waste.Along with the fast development of industry, efficiently utilizing of micro crystal graphite is particularly important.For make micro crystal graphite this
Dominant Mineral Resources obtains abundant Efficient Development and utilizes, it is necessary to it is carried out High Purity research.
Purify micro crystal graphite method at present and mainly have chemical method and high temperature method.Chemical method mainly comprises alkali fusion, chlorination roasting
Burning method and mixed acid process；The fixed carbon content of the graphite that alkali fusion and chlorinating roasting purify is difficult to reach more than 99.9%.Mixed acid process
Refer to, by Fluohydric acid. and the nitration mixture such as hydrochloric acid, sulphuric acid, mix according to a certain ratio with graphite, stir and heat treatment, finally can fix
The method of the high purity graphite of carbon content more than 99.95%.But owing to volatility and the severe corrosive of Fluohydric acid. cause environmental pollution non-
Chang great, belongs to high pollution.High temperature method refers to be heated to graphite in graphitizing furnace more than 2700 DEG C, removes the volatilization in graphite
Divide and ash, thus purification obtains fixed carbon content and reaches the high purity graphite method of more than 99.9%.High temperature method power consumption is big, energy consumption
The highest, cost is high.These methods do not comply with the energy-saving and emission-reduction policy of country at present, the most do not have considerable prospect.
Summary of the invention
The present invention is directed to existing technical problem, it is provided that the method for purification of a kind of micro crystal graphite, the method is by be purified
Micro crystal graphite powder be placed in supercritical fluid purification, the method is easy and simple to handle, pollute little, economical and efficient.
For achieving the above object, the present invention provides following technical scheme: the method for purification of a kind of micro crystal graphite, its feature exists
In, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 2～15:1, the micro crystal graphite that mass fraction is 70%～90% of phosphorus content is added
Mass percent concentration is in the aqueous solution of 100% purification gas, is subsequently placed in high-pressure reactor, is sufficiently stirred for, airtight, adjusts
Whole temperature and pressure, makes purification gas enter supercriticality, and leaching 20～90min, is cooled to room temperature, lets out in the reactor
It is depressed into atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite after purification step (1) obtained separates with waste liquid centrifugal separator, then by microlite ink
Washing pH value is 6.5, dries afterwards and i.e. can get high-purity micro crystal graphite under the temperature conditions of 120 DEG C.
Further, as preferably, the gas that purifies described in described step (1) is at least one in hydrogen chloride, chlorine,
Supercritical temperature and pressure that hydrogen chloride is corresponding are 51.4 DEG C, 8.26MPa, and supercritical temperature and pressure that chlorine is corresponding are 144
℃、7.71Mpa。
Further, as preferably, in described step (2), when using centrifugal separator to separate, the rotating speed of centrifugal separator
Being 100～3000 revs/min, the time is 1～20 minute.
Further, as preferably, after described step (2), also include that the waste liquid employing distillation under vacuum by separating will
Purify collection and confinement of gases and go out to enter the step that high-pressure reactor reuses.
Further, as preferably, in described step (2), liquid-solid separator or filter is used to replace centrifugation
Machine realizes the micro crystal graphite after purifying and the separation of waste liquid.
Compared with prior art, the invention has the beneficial effects as follows:
(1) present invention uses the purification gas of supercriticality to purify micro crystal graphite, the purification gas under supercriticality
The high osmosis of body and solvability ensure that the removal of graphite raw material deep level impurity, thus reach preferable refining effect,
Micro crystal graphite fixed carbon content after final purification may be up to more than 99.99, and iron content is less than 10ppm.
(2) method of purification of this micro crystal graphite is simple to operate, and purifying gas can recycle, and workable, has
Considerable application prospect.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
Embodiment one
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 10:1, the micro crystal graphite that phosphorus content mass fraction is 80% is added mass percent
Concentration is in the hydrochloride aqueous solution of 100%, and wherein, supercritical temperature and pressure that hydrogen chloride is corresponding are 51.4 DEG C, 8.26MPa,
It is subsequently placed in high-pressure reactor, is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality,
Reactor soaks 60min, is cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite and waste liquid centrifugal separator after purification step (1) obtained separate, and rotating speed is 2000
Rev/min, the time is 12 minutes, and it is 6.5 that micro crystal graphite is then washed pH value, dries afterwards under the temperature conditions of 120 DEG C
I.e. can get high-purity micro crystal graphite, purification collection and confinement of gases is gone out to enter high-pressure reactor by waste liquid employing distillation under vacuum to be made again
With.
Embodiment two
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 5:1, the micro crystal graphite that phosphorus content mass fraction is 75% is added mass percent
Concentration is in the aqueous solution of the chlorine of 100%, and wherein, supercritical temperature and pressure that chlorine is corresponding are 144 DEG C, 7.71Mpa, so
It is placed in high-pressure reactor, is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality, instead
Answer leaching 80min in device, be cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite and waste liquid centrifugal separator after purification step (1) obtained separate, and rotating speed is 1500
Rev/min, the time is 10 minutes, and it is 6.5 that micro crystal graphite is then washed pH value, dries afterwards under the temperature conditions of 120 DEG C
I.e. can get high-purity micro crystal graphite, purification collection and confinement of gases is gone out to enter high-pressure reactor by waste liquid employing distillation under vacuum to be made again
With.
Embodiment three
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 3:1, the micro crystal graphite that phosphorus content mass fraction is 90% is added mass percent
Concentration is in the hydrochloride aqueous solution of 100%, and wherein, supercritical temperature and pressure that hydrogen chloride is corresponding are 51.4 DEG C, 8.26MPa,
It is subsequently placed in high-pressure reactor, is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality,
Reactor soaks 20min, is cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite and waste liquid centrifugal separator after purification step (1) obtained separate, and rotating speed is 1000
Rev/min, the time is 20 minutes, and it is 6.5 that micro crystal graphite is then washed pH value, dries afterwards under the temperature conditions of 120 DEG C
I.e. can get high-purity micro crystal graphite, purification collection and confinement of gases is gone out to enter high-pressure reactor by waste liquid employing distillation under vacuum to be made again
With.
Embodiment four
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 15:1, the micro crystal graphite that phosphorus content mass fraction is 75% is added mass percent
Concentration is that in the hydrogen chloride of 100% and the aqueous solution of chlorine mixing, wherein, supercritical temperature and pressure that hydrogen chloride is corresponding are
51.4 DEG C, 8.26MPa, supercritical temperature and pressure that chlorine is corresponding are 144 DEG C, 7.71Mpa, are subsequently placed in high-pressure reactor
In, it is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality, soak 30min in the reactor, then
It is cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite and waste liquid centrifugal separator after purification step (1) obtained separate, and rotating speed is 3000
Rev/min, the time is 5 minutes, and it is 6.5 that micro crystal graphite is then washed pH value, dries afterwards under the temperature conditions of 120 DEG C
I.e. can get high-purity micro crystal graphite, purification collection and confinement of gases is gone out to enter high-pressure reactor by waste liquid employing distillation under vacuum to be made again
With.
Embodiment five
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 8:1, the micro crystal graphite that phosphorus content mass fraction is 85% is added mass percent
Concentration is in the aqueous solution of the chlorine of 100%, and wherein, supercritical temperature and pressure that chlorine is corresponding are 144 DEG C, 7.71Mpa, so
It is placed in high-pressure reactor, is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality, instead
Answer leaching 50min in device, be cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite and waste liquid centrifugal separator after purification step (1) obtained separate, and rotating speed is 1400
Rev/min, the time is 12 minutes, and it is 6.5 that micro crystal graphite is then washed pH value, dries afterwards under the temperature conditions of 120 DEG C
I.e. can get high-purity micro crystal graphite, purification collection and confinement of gases is gone out to enter high-pressure reactor by waste liquid employing distillation under vacuum to be made again
With.
Embodiment six
A kind of method of purification of micro crystal graphite, it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 12:1, the micro crystal graphite that phosphorus content mass fraction is 88% is added mass percent
Concentration is in the hydrochloride aqueous solution of 100%, and wherein, supercritical temperature and pressure that hydrogen chloride is corresponding are 51.4 DEG C, 8.26MPa,
It is subsequently placed in high-pressure reactor, is sufficiently stirred for, airtight, adjust temperature and pressure, make purification gas enter supercriticality,
Reactor soaks 40min, is cooled to room temperature, pressure release to atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite after purification step (1) obtained and waste liquid liquid-solid separator or filter separate, then
It is 6.5 that micro crystal graphite is washed pH value, dries afterwards and i.e. can get high-purity micro crystal graphite, waste liquid under the temperature conditions of 120 DEG C
Distillation under vacuum is used to go out to enter high-pressure reactor by purification collection and confinement of gases and reuse.
Comparative example one
Use the micro crystal graphite raw material as a comparison case 1 that mixed acid process purifies.
Comparative example two
Use the micro crystal graphite raw material as a comparison case 2 that high temperature method purifies.
Use GB/T 3521-2008 graphite chemical analysis method testing example 1-6 and comparative example 1-2 ash below.
Germany SPECTRO BLUE SOP is used entirely to compose direct-reading plasma emission spectrometer testing example 1-6 and right
Ratio 1-2 impurity content.
The data obtained are as shown in table 1 below.
The performance parameter of the micro crystal graphite that table 1 lists the embodiment of the present invention and comparative example purification compares.
| Embodiment/comparative example | Ash/% | Fe content/ppm | Ca content/ppm | Si content/ppm |
| Embodiment 1 | 99.992 | 6 | 8 | 5 |
| Embodiment 2 | 99.994 | 4 | 10 | 3 |
| Embodiment 3 | 99.996 | 3- | 6 | 4 |
| Embodiment 4 | 99.995 | 5 | 11 | 2 |
| Embodiment 5 | 99.996 | 4 | 7 | 1 |
| Embodiment 6 | 99.996 | 3 | 2 | 5 |
| Comparative example 1 | 99.953 | 38 | 78 | 30 |
| Comparative example 2 | 99.982 | 17 | 15 | 3 |
As can be seen from the above results: the micro crystal graphite purity that the embodiment of the present invention purifies is higher, and impurity content is lower, greatly
Improve greatly technology content and the range of application of micro crystal graphite.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, permissible
Understand and these embodiments can be carried out multiple change without departing from the principles and spirit of the present invention, revise, replace
And modification, the scope of the present invention be defined by the appended.
Claims (5)
1. the method for purification of a micro crystal graphite, it is characterised in that it comprises the following steps: it comprises the following steps:
(1) in the ratio that liquid-solid mass ratio is 2～15:1, the micro crystal graphite that mass fraction is 70%～90% of phosphorus content is added
Mass percent concentration is in the aqueous solution of 100% purification gas, is subsequently placed in high-pressure reactor, is sufficiently stirred for, airtight, adjusts
Whole temperature and pressure, makes purification gas enter supercriticality, and leaching 20～90min, is cooled to room temperature, lets out in the reactor
It is depressed into atmospheric pressure, the micro crystal graphite after being purified and waste liquid；
(2) micro crystal graphite after purification step (1) obtained separates with waste liquid centrifugal separator, then by microlite ink
Washing pH value is 6.5, dries afterwards and i.e. can get high-purity micro crystal graphite under the temperature conditions of 120 DEG C.
The method of purification of a kind of micro crystal graphite the most according to claim 1, it is characterised in that: described in described step (1)
Purify gas be at least one in hydrogen chloride, chlorine, wherein, supercritical temperature and pressure that hydrogen chloride is corresponding are 51.4
DEG C, 8.26MPa, supercritical temperature and pressure that chlorine is corresponding are 144 DEG C, 7.71Mpa.
The method of purification of a kind of micro crystal graphite the most according to claim 1, it is characterised in that: in described step (2), adopt
When separating with centrifugal separator, the rotating speed of centrifugal separator is 100～3000 revs/min, and the time is 1～20 minute.
The method of purification of a kind of micro crystal graphite the most according to claim 1, it is characterised in that: after described step (2), also wrap
Include and the waste liquid separated uses distillation under vacuum go out to enter, by purifying collection and confinement of gases, the step that high-pressure reactor reuses.
The method of purification of a kind of micro crystal graphite the most according to claim 1, it is characterised in that: in described step (2), adopt
Replace centrifugal separator with liquid-solid separator or filter and realize the micro crystal graphite after purifying and the separation of waste liquid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395726A (en) * | 2019-09-04 | 2019-11-01 | 湖南有色金属研究院 | A kind of method of purification of micro crystal graphite mine |
| CN113149001A (en) * | 2021-03-05 | 2021-07-23 | 大同氢都驰拓新能源有限公司 | Automatic high-yield method for preparing and purifying spherical graphite |
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| CN101712469A (en) * | 2008-09-30 | 2010-05-26 | 韩华石油化学株式会社 | Continuous method and apparatus of purifying carbon nanotube |
| JP2011037693A (en) * | 2008-09-26 | 2011-02-24 | Vision Development Co Ltd | Method for refining nanodiamond and refined nanodiamond |
| CN103435030A (en) * | 2013-07-11 | 2013-12-11 | 中国石油大学(北京) | Preparation apparatus and preparation method for graphene |
| CN105271216A (en) * | 2015-12-07 | 2016-01-27 | 湖南顶立科技有限公司 | Preparation method of high-purity graphite |
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- 2016-07-19 CN CN201610568679.3A patent/CN106219526B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011037693A (en) * | 2008-09-26 | 2011-02-24 | Vision Development Co Ltd | Method for refining nanodiamond and refined nanodiamond |
| CN101712469A (en) * | 2008-09-30 | 2010-05-26 | 韩华石油化学株式会社 | Continuous method and apparatus of purifying carbon nanotube |
| CN103435030A (en) * | 2013-07-11 | 2013-12-11 | 中国石油大学(北京) | Preparation apparatus and preparation method for graphene |
| CN105271216A (en) * | 2015-12-07 | 2016-01-27 | 湖南顶立科技有限公司 | Preparation method of high-purity graphite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110395726A (en) * | 2019-09-04 | 2019-11-01 | 湖南有色金属研究院 | A kind of method of purification of micro crystal graphite mine |
| CN113149001A (en) * | 2021-03-05 | 2021-07-23 | 大同氢都驰拓新能源有限公司 | Automatic high-yield method for preparing and purifying spherical graphite |
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