CN106219526B - 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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- CN106219526B CN106219526B CN201610568679.3A CN201610568679A CN106219526B CN 106219526 B CN106219526 B CN 106219526B CN 201610568679 A CN201610568679 A CN 201610568679A CN 106219526 B CN106219526 B CN 106219526B
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- 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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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a kind of methods of purification of micro crystal graphite, this method is that micro crystal graphite is placed in high-pressure reactor, it is sufficiently stirred, it is closed, adjust temperature and pressure, purification gas is set to enter supercriticality, 20~90min is soaked in the reactor, it is cooled to room temperature, pressure release is to atmospheric pressure, then micro crystal graphite and waste liquid are separated, washing, high-purity micro crystal graphite can be obtained in drying, the fixed carbon content of micro crystal graphite after final purification may be up to 99.99 or more, iron content is less than 10ppm, the method of purification is easy to operate, purification gas can be recycled, it is low in cost, there is considerable application prospect.
Description
Technical field
The present invention relates to graphite purification fields, and in particular to a kind of method of purification of micro crystal graphite.
Background technique
Natural micro crystal graphite is a kind of mineral products of China's rich reserves, its particle is the small crystalline substance by many random orientations
Body is assembled, and is in isotropism.Its reserves is more than 200,000,000 t, and fixed carbon content is mostly 75% ~ 90%, industrially mostly directly
It is with low content of technology using high-grade raw ore, it produces and sells with crude product mostly, resource is not fully utilized, and causes resource
Serious waste.With the rapid development of industry, efficient utilize of micro crystal graphite is particularly important.For make micro crystal graphite this
Dominant Mineral Resources obtain sufficiently efficiently development and utilization, it is necessary to carry out High Purity research to it.
Purification micro crystal graphite method mainly has chemical method and high temperature method at present.Chemical method mainly includes alkali fusion, chlorination roasting
Burning method and mixed acid process；The fixation carbon content of alkali fusion and the graphite of chlorinating roasting purification is difficult to reach 99.9% or more.Mixed acid process
Refer to the nitration mixture such as hydrofluoric acid and hydrochloric acid, sulfuric acid, mix, stir and be heat-treated according to a certain ratio with graphite, can finally obtain fixed
The method of the high purity graphite of 99.95% or more carbon content.But the volatility and strong corrosive due to hydrofluoric acid cause environmental pollution non-
Chang great belongs to high pollution.High temperature method refers to is heated to graphite 2700 DEG C or more in graphitizing furnace, removes the volatilization in graphite
Point and ash content, so that purification obtains fixed carbon content up to 99.9% or more high purity graphite method.High temperature method power consumption is big, energy consumption
It is very high, it is at high cost.These methods do not comply with the energy-saving and emission-reduction policy of country at present, therefore do not have considerable prospect.
Summary of the invention
Present invention problem in view of the prior art, provides a kind of method of purification of micro crystal graphite, this method is will be to be purified
Micro crystal graphite powder be placed in supercritical fluid and purify, this method is easy to operate, pollution is small, economical and efficient.
To achieve the above object, the present invention provides the following technical solutions：A kind of method of purification of micro crystal graphite, feature exist
In comprising following steps：
（1）Consolidating mass ratio by liquid is 2~15:The micro crystal graphite that the mass fraction of phosphorus content is 70%~90% by 1 ratio
It is added in the aqueous solution that mass percent concentration is 100% purification gas, is subsequently placed in high-pressure reactor, is sufficiently stirred, it is close
It closes, adjusts temperature and pressure, so that purification gas is entered supercriticality, soak 20~90min in the reactor, be cooled to room
Temperature, pressure release to atmospheric pressure, micro crystal graphite and waste liquid after being purified；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, then by microlite
It is 6.5 that ink, which washes pH value, and high-purity micro crystal graphite can be obtained in drying under the conditions of 120 DEG C of temperature later.
Further, preferably, the step（1）Described in purification gas be at least one of hydrogen chloride, chlorine,
The corresponding supercritical temperature of hydrogen chloride and pressure are 51.4 DEG C, 8.26MPa, and the corresponding supercritical temperature of chlorine and pressure are 144
℃、7.71Mpa。
Further, preferably, in the step（2）In, when being separated using centrifugal separator, the revolving speed of centrifugal separator
It is 100~3000 revs/min, the time is 1~20 minute.
Further, preferably, the step（2）Afterwards, further including will using distillation under vacuum by the waste liquid separated
Purification gas collection goes out the step of reusing into high-pressure reactor.
Further, preferably, in the step（2）In, centrifuge separation is replaced using liquid-solid separator or filter
Machine come realize purification after micro crystal graphite and waste liquid separation.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）The present invention purifies micro crystal graphite using the purification gas of supercriticality, mentioning under supercriticality
The high osmosis and solvability of pure gas can guarantee the removal of graphite raw material deep level impurity, to reach ideal purification effect
Fruit, the fixed carbon content of micro crystal graphite after final purification may be up to 99.99 or more, and iron content is less than 10ppm.
（2）The method of purification of the micro crystal graphite is easy to operate, and purification gas can be recycled, and strong operability, has
Considerable application prospect.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment one
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 10:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 80% by 1 ratio
In the hydrochloride aqueous solution that point specific concentration is 100%, wherein the corresponding supercritical temperature of hydrogen chloride and pressure is 51.4 DEG C,
8.26MPa is subsequently placed in high-pressure reactor, is sufficiently stirred, closed, adjusts temperature and pressure, and purification gas is made to enter super face
Boundary's state, soaks 60min in the reactor, is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite after being purified and useless
Liquid；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, and revolving speed is
2000 revs/min, the time is 12 minutes, is then 6.5 by micro crystal graphite washing pH value, later under the conditions of 120 DEG C of temperature
High-purity micro crystal graphite can be obtained in drying, and waste liquid goes out to enter high-pressure reactor again using distillation under vacuum by gas collection is purified
It uses.
Embodiment two
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 5:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 75% by 1 ratio
In the aqueous solution for the chlorine that point specific concentration is 100%, wherein the corresponding supercritical temperature of chlorine and pressure is 144 DEG C,
7.71Mpa is subsequently placed in high-pressure reactor, is sufficiently stirred, closed, adjusts temperature and pressure, and purification gas is made to enter super face
Boundary's state, soaks 80min in the reactor, is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite after being purified and useless
Liquid；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, and revolving speed is
1500 revs/min, the time is 10 minutes, is then 6.5 by micro crystal graphite washing pH value, later under the conditions of 120 DEG C of temperature
High-purity micro crystal graphite can be obtained in drying, and waste liquid goes out to enter high-pressure reactor again using distillation under vacuum by gas collection is purified
It uses.
Embodiment three
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 3:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 90% by 1 ratio
In the hydrochloride aqueous solution that point specific concentration is 100%, wherein the corresponding supercritical temperature of hydrogen chloride and pressure is 51.4 DEG C,
8.26MPa is subsequently placed in high-pressure reactor, is sufficiently stirred, closed, adjusts temperature and pressure, and purification gas is made to enter super face
Boundary's state, soaks 20min in the reactor, is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite after being purified and useless
Liquid；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, and revolving speed is
1000 revs/min, the time is 20 minutes, is then 6.5 by micro crystal graphite washing pH value, later under the conditions of 120 DEG C of temperature
High-purity micro crystal graphite can be obtained in drying, and waste liquid goes out to enter high-pressure reactor again using distillation under vacuum by gas collection is purified
It uses.
Example IV
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 15:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 75% by 1 ratio
Divide in the hydrogen chloride and chlorine mixed aqueous solutions that specific concentration is 100%, wherein the corresponding supercritical temperature of hydrogen chloride and pressure
For 51.4 DEG C, 8.26MPa, the corresponding supercritical temperature of chlorine and pressure are 144 DEG C, 7.71Mpa, are subsequently placed in high-pressure reactor
In, it is sufficiently stirred, it is closed, temperature and pressure is adjusted, so that purification gas is entered supercriticality, soaks 30min in the reactor, then
It is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite and waste liquid after being purified；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, and revolving speed is
3000 revs/min, the time is 5 minutes, is then 6.5 by micro crystal graphite washing pH value, later under the conditions of 120 DEG C of temperature
High-purity micro crystal graphite can be obtained in drying, and waste liquid goes out to enter high-pressure reactor again using distillation under vacuum by gas collection is purified
It uses.
Embodiment five
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 8:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 85% by 1 ratio
In the aqueous solution for the chlorine that point specific concentration is 100%, wherein the corresponding supercritical temperature of chlorine and pressure is 144 DEG C,
7.71Mpa is subsequently placed in high-pressure reactor, is sufficiently stirred, closed, adjusts temperature and pressure, and purification gas is made to enter super face
Boundary's state, soaks 50min in the reactor, is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite after being purified and useless
Liquid；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, and revolving speed is
1400 revs/min, the time is 12 minutes, is then 6.5 by micro crystal graphite washing pH value, later under the conditions of 120 DEG C of temperature
High-purity micro crystal graphite can be obtained in drying, and waste liquid goes out to enter high-pressure reactor again using distillation under vacuum by gas collection is purified
It uses.
Embodiment six
A kind of method of purification of micro crystal graphite comprising following steps：
（1）Consolidating mass ratio by liquid is 12:Quality hundred is added in the micro crystal graphite that phosphorus content mass fraction is 88% by 1 ratio
In the hydrochloride aqueous solution that point specific concentration is 100%, wherein the corresponding supercritical temperature of hydrogen chloride and pressure is 51.4 DEG C,
8.26MPa is subsequently placed in high-pressure reactor, is sufficiently stirred, closed, adjusts temperature and pressure, and purification gas is made to enter super face
Boundary's state, soaks 40min in the reactor, is cooled to room temperature, pressure release to atmospheric pressure, micro crystal graphite after being purified and useless
Liquid；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with liquid-solid separator or filter,
It then is 6.5 by micro crystal graphite washing pH value, high-purity micro crystal graphite can be obtained in drying under the conditions of 120 DEG C of temperature later,
Waste liquid will purify gas collection using distillation under vacuum and go out into high-pressure reactor to reuse.
Comparative example one
Using the micro crystal graphite raw material as a comparison case 1 of mixed acid process purification.
Comparative example two
Using the micro crystal graphite raw material as a comparison case 2 of high temperature method purification.
GB/T 3521-2008 graphite chemical analysis method testing example 1-6 and comparative example 1-2 ash content are used below.
Direct-reading plasma emission spectrometer testing example 1-6 and right is composed using German SPECTRO BLUE SOP entirely
Ratio 1-2 impurity content.
Obtained data are as shown in table 1 below.
The performance parameter that table 1 lists the micro crystal graphite of the embodiment of the present invention and comparative example purification compares.
| Embodiment/comparative example | Ash content/% | 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 of purification of the embodiment of the present invention is higher, and impurity content is lower, greatly
The technology content and application range of micro crystal graphite are improved greatly.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (3)
1. a kind of method of purification of micro crystal graphite, which is characterized in that it includes the following steps：
（1）Consolidating mass ratio by liquid is 2~15:The micro crystal graphite that the mass fraction of phosphorus content is 70%~90% is added 1 ratio
Mass percent concentration is to be subsequently placed in high-pressure reactor, be sufficiently stirred in the aqueous solution of 100% purification gas, closed, is adjusted
Whole temperature and pressure makes purification gas enter supercriticality, soaks 20~90min in the reactor, be cooled to room temperature, pressure release
To atmospheric pressure, micro crystal graphite and waste liquid after being purified；
（2）By step（1）Micro crystal graphite and waste liquid after obtained purification are separated with centrifugal separator, then by microlite ink
Being washed till pH value is 6.5, and high-purity micro crystal graphite can be obtained in drying under the conditions of 120 DEG C of temperature later；
The step（1）Described in purification gas be at least one of hydrogen chloride, chlorine, wherein hydrogen chloride is corresponding super
Critical-temperature and pressure are 51.4 DEG C, 8.26MPa, and the corresponding supercritical temperature of chlorine and pressure are 144 DEG C, 7.71MP a.
2. a kind of method of purification of micro crystal graphite according to claim 1, it is characterised in that：In the step（2）In, it adopts
When being separated with centrifugal separator, the revolving speed of centrifugal separator is 100~3000 revs/min, and the time is 1~20 minute.
3. a kind of method of purification of micro crystal graphite according to claim 1, it is characterised in that：The step（2）Afterwards, it also wraps
It includes and the waste liquid separated is gone out into the step of reusing into high-pressure reactor for gas collection is purified using distillation under vacuum.
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| 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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