CN107601496A - A kind of nuclear graphite and preparation method thereof based on micro crystal graphite for raw material - Google Patents
A kind of nuclear graphite and preparation method thereof based on micro crystal graphite for raw material Download PDFInfo
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Abstract
The present invention relates to micro crystal graphite production technical field, discloses a kind of based on nuclear graphite that micro crystal graphite is raw material and preparation method thereof.The present invention using aphanitic graphite prepare nuclear graphite have very high thermal conductivity, the graphitization of height, low each same tropism than with higher bending strength, various coke compared with prior art, the present invention can be readily available isotropism than the isotropic graphite for 1.1~1.15 by isostatic pressed, and the green compact thermal diffusivity of micro crystal graphite is significantly larger than the green compact of coke powder, so as to be more beneficial for being calcined.Ash content and boron equivalent meet the impurity requirement of nuclear graphite in the nuclear graphite impurity that the present invention is prepared.
Description
Technical field
The present invention relates to micro crystal graphite production technical field, more particularly, to it is a kind of based on micro crystal graphite be raw material
Nuclear graphite and preparation method thereof.
Background technology
Graphite is a kind of high energy crystal carbon material, because of its unique structure and conduction, heat conduction, lubrication, high temperature resistant, chemically
Can be stable the features such as, be widely used in metallurgy, machinery, environmental protection, chemical industry, fire resisting, new energy, nuclear energy, electronics, medicine, military project and
The fields such as Aero-Space.
Native graphite shaping geological conditions in China is good, widely distributed, aboundresources, quality are good, and reserves and yield all occupy generation
Boundary is the first, is one of the Dominant Mineral Resources in China.Native graphite can be divided into Scaly graphite and microcrystalline according to the difference of crystallization degree
The class of graphite two, wherein Chenzhou aphanitic graphite account for 74.7% or so of national gross reserves, and the aphanitic graphite quality is preferable,
Fixed carbon content is high, there is good isotropism.
But for a long time, people mostly pay attention to the exploitation and processing of Scaly graphite, ignore and occupy a greater part of reserves
The utilization of microcrystalline graphite, the problem of its deep process technology is horizontal and deep processing ability is relatively low, are not solved effectively for a long time
Certainly.At present mainly based on raw ore and rough-wrought product application, resource is not fully utilized, or even blindly exports, and causes ore deposit
The a large amount of losses and waste of resource are produced, the primary stages such as raw material is confined to using aphanitic graphite at present, is generally used for pencil,
Crucible and the carburizer for steel-making, therefore, it is necessary to being further based on micro crystal graphite develops more high-end application.
Nuclear graphite be for nuclear industry in terms of graphite material.There are atomic pile neutron moderator, reflective agent, production
The plume graphite of isotope, the globular graphite of HTGR and blocky graphite etc..Current commercialized nuclear graphite by
Various coke type productions, on the application of native graphite, wherein crystalline flake graphite has been successfully applied to HTR- ball fuels member
Part, but never it is directed to relevant report and research of the aphanitic graphite in nuclear graphite field.
The content of the invention
There is good isotropism for current natural micro crystal graphite, the typically fixed carbon content of micro crystal graphite raw ore compared with
Height, but impurity content is complicated, purification difficult, application surface is narrower, is not utilized for a long time, and the present invention is using micro crystal graphite as original
Material, is improved on existing purifying technique, fully reduces the energy consumption and cost of purification, there is provided a kind of inexpensive, low energy consumption
Based on the nuclear graphite preparation method that micro crystal graphite is raw material.
The purpose of the present invention is achieved by the following technical programs：
A kind of nuclear graphite preparation method based on micro crystal graphite for raw material is provided, comprised the following steps：
S1. raw ore is handled：It is 75~80% micro crystal graphite crushing raw ores by fixed carbon content, then to micro crystal graphite raw ore
Depth ore grinding is carried out, it is -0.074mm level materials to obtain fineness by ore grinding, is -0.074mm level material contents to mog
The primary sample for accounting for 90% carries out flotation, using four selected once purging selection flows of one roughing, dries afterwards, magnetic separation, consolidate
It is 85~90% micro crystal graphites to determine carbon content；
S2. acidleach purifies：
S21. microlite ink powder obtained by step S1 is heat-treated at 600~800 DEG C, 1~3min of time；
S22. the mineral after step S2 is heat-treated while hot mix with aqueous slkali, ore pulp liquid-solid ratio 10~12:1, ultrasound
30min, alkaline pressure of oxygen leaching is then carried out under conditions of 100~110 DEG C of temperature, 2~3h of reaction time, leached mud is through washing, doing
Alkali leaching graphite is obtained after dry；
S23. alkali obtained by step S3 being soaked into graphite and acid mixes, the acid uses hydrochloric acid or sulfuric acid, ore pulp liquid-solid ratio 10~
12:1, ultrasonic 30min, normal pressure acidleach, leached mud are then carried out under conditions of 100~110 DEG C of temperature, 2~3h of reaction time
Cleaned when graphite to rinsing solution is neutrality and precipitated with distilled water or deionized water, then filtered, dry, obtain graphite powder, Gu
Carbon content is determined for more than 99%；
S3. high temperature method purifies：Graphite powder is directly loadable into graphite crucible, is being passed through the purifying of inert gas and protective gas
Using heating up step by step in stove, temperature is risen to 2500~2700 DEG C first, the heat time is 20~30min, is then heated to
2750~3000 DEG C, the heat time is 30~40min, is then progressively cooled to room temperature, is fixed carbon content as 99.993%
High-purity micro crystal graphite above；
S4. separating twice：High-purity micro crystal graphite that step S3 is obtained carries out ball milling, screening again, obtains median
D5040 μm of high-purity micro crystal graphite；
S5. isostatic pressing：Step S4 products obtained therefroms are fitted into rubber mold, are then placed in iso-static pressure shaping machine
Row shaping, pressure is 100~300MPa；
S6. it is calcined：By step S5 products obtained therefroms in atmosphere of inert gases, it is calcined at 800~1000 DEG C, then pass through
Density is brought up to 1.78g/m by dipping with heavily doped3More than；
S7. graphitization：Step S6 products obtained therefroms are inserted in graphitizing furnace, are heated to 1000 first with 20~30 DEG C/min
DEG C, 2800 DEG C then are heated to 10 DEG C/min again, 10h is kept, then naturally cools to room temperature, finally give based on microlite
Ink is the nuclear graphite of raw material.
Preferably, the micro crystal graphite raw ore is Shandong pool graphite, wherein moisture 2.4%, volatile matter 2.99%, ash content
18.37% carbon content 78.64%, further solve the problems, such as that aphanitic graphite non-long period of development in Chenzhou utilizes.
Preferably, aqueous slkali described in step S22 is sodium hydroxide solution, the concentration of sodium hydroxide solution is 10~
30%.
Preferably, ore pulp liquid-solid ratio described in step S22 is 11:1, temperature is 105 DEG C, reacts 2.5h, the pressurization alkali
Pressure is 0.6~0.8MPa during leaching.
Preferably, drying described in step S22 and step S23 is to dry 2~3h, step in the case where temperature is 80~150 DEG C
Ore pulp liquid-solid ratio described in S23 is 11:1, temperature is 115 DEG C, reacts 2.5h；The acid is hydrochloric acid or sulfuric acid, and concentration of hydrochloric acid is
2%~37%, sulfuric acid concentration is 7%~98%.
Preferably, pressure described in step S5 is 200MPa.
Preferably, inert gas described in step S6 is nitrogen.
Preferably, sintering temperature is 1000 DEG C in step S6.
Preferably, 1000 DEG C are heated to 25 DEG C/min first in step S7.
The present invention also provides a kind of nuclear graphite being prepared using the above method.
Compared with prior art, the beneficial effects of the invention are as follows：
The nuclear graphite that the present invention is prepared using aphanitic graphite has the very high thermal conductivity, graphitization of height, low each
With tropism than that can be readily available by isostatic pressed with higher bending strength, compared with prior art various coke, the present invention
Isotropism is than the isotropic graphite for 1.1~1.15, and the green compact thermal diffusivity of micro crystal graphite is significantly larger than coke powder
Green compact, so as to be more beneficial for being calcined.Ash content and boron equivalent meet the miscellaneous of nuclear graphite in the nuclear graphite impurity that the present invention is prepared
Matter requirement.
Brief description of the drawings
Fig. 1 flotation flowsheet figures.
Fig. 2 Shandongs pool aphanitic graphite transmission electron microscope photo.
Fig. 3 Shandongs pool aphanitic graphite structural representation.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The present embodiment provides a kind of nuclear graphite preparation method based on micro crystal graphite for raw material, comprises the following steps：
S1. raw ore is handled：By micro crystal graphite crushing raw ore, depth ore grinding then is carried out to micro crystal graphite raw ore, passes through mill
It is -0.074mm level materials that ore deposit, which obtains fineness, is that -0.074mm level material contents account for 90% primary sample and floated to mog
Choosing, using four selected once purging selection flows of one roughing, afterwards drying, magnetic separation, it is 90% microlite to be fixed carbon content
Ink；
Micro crystal graphite raw ore is Shandong pool graphite, wherein moisture 2.4% in the processing of the present embodiment raw ore, volatile matter 2.99%,
The carbon content 78.64% of ash content 18.37%；
S2. acidleach purifies：
S21. microlite ink powder obtained by step S1 is heat-treated at 500~600 DEG C, time 1min；
S22. the mineral after step S2 is heat-treated while hot mix with aqueous slkali, ore pulp liquid-solid ratio 10:1, ultrasound
30min, then carries out alkaline pressure of oxygen leaching under conditions of 100 DEG C of temperature, reaction time 2h, and leached mud obtains through washing, after drying
Alkali soaks graphite；
S23. alkali obtained by step S3 is soaked into graphite and acid mixes, the acid uses hydrochloric acid or sulfuric acid, ore pulp liquid-solid ratio 10:1,
Ultrasonic 30min, normal pressure acidleach is then carried out under conditions of 100 DEG C of temperature, reaction time 2h, leached mud distilled water or is gone
Ionized water clean graphite to rinsing solution for it is neutral when precipitate, then filter, dry, obtain graphite powder, fixed carbon content is
99.23%；
The present embodiment aqueous slkali is sodium hydroxide solution, and the concentration of sodium hydroxide solution is 10%；Alkaline pressure of oxygen leaching process
Middle pressure is 0.6MPa, and the acid is hydrochloric acid or sulfuric acid, concentration of hydrochloric acid 2%, sulfuric acid concentration 7%.
Drying described in the present embodiment step S22 and step S23 is to dry 2~3h in the case where temperature is 80~150 DEG C.
S3. high temperature method purifies：Graphite powder is directly loadable into graphite crucible, is being passed through the purifying of inert gas and protective gas
Using heating up step by step in stove, temperature is risen to 2500~2700 DEG C first, the heat time is 20~30min, is then heated to
2750~3000 DEG C, the heat time is 30~40min, is then progressively cooled to room temperature, is fixed carbon content as 99.993%
High-purity micro crystal graphite；
S4. separating twice：High-purity micro crystal graphite that step S3 is obtained carries out ball milling, screening again, obtains median
D5040 μm of high-purity micro crystal graphite；
S5. isostatic pressing：Step S4 products obtained therefroms are fitted into rubber mold, are then placed in iso-static pressure shaping machine
Row shaping, pressure 100MPa；
S6. it is calcined：By step S5 products obtained therefroms in atmosphere of inert gases, be calcined at 800 DEG C, then by dipping and
It is heavily doped that density is brought up into 1.78g/m3More than；
S7. graphitization：Step S6 products obtained therefroms are inserted in graphitizing furnace, are heated to 1000 DEG C first with 20 DEG C/min,
Then 2800 DEG C are heated to 10 DEG C/min again, keep 10h, then naturally cool to room temperature, finally give based on micro crystal graphite
For the nuclear graphite of raw material.
Step S1 carries out crystallite stone mill raw ore and is crushed and ground first, coordinates the one roughing four times selected one of flotation
It is secondary to scan flow, at utmost by physical method improve raw ore purity (fixed carbon content be 85~90% micro crystal graphites such as
Fruit will also make its grade be further enhanced, and floatation is all than relatively difficult to achieve in technology or economically) simultaneously
Micro crystal graphite particle diameter is reduced, increases the specific surface area of micro crystal graphite, is advantageous to follow-up acidleach purification and gasification, reduces subsequent purification
Energy consumption and cost.
Step S2 acidleach purification first carries out high temperature pretreatment to the raw ore after processing, then enters to carry out acid-base method while hot to micro-
Brilliant graphite ore is purified, and in acid-base method conventional process, the present invention substitutes HF using sulfuric acid or hydrochloric acid, and using pressurization alkali
Leaching substitutes high-temperature calcination, while coordinates the microlite ore grinding after heat treatment to reduce alkali leaching temperature in acid-base method purification process
Degree, alkali leaching efficiency is improved, energy consumption can be reduced, while also improve recycling graphite rate, in addition, the present invention is also creatively in acid
Preferred ore pulp liquid-solid ratio before alkaline reaction, add ultrasonication so that micro crystal graphite is additionally separated with impurity, so as to carry
The fixed carbon content of height, meanwhile, the scrubbing action of ultrasonic wave makes particle surface polish, and its cardinal principle is in ultrasonic procedure
Mechanical crushing acts on and cavitation can crush micro crystal graphite particle, makes to be wrapped in the partial impurities in aggregate and participates in instead
Should, the reaction rate of impurity and soda acid is accelerated, further increasing fixed carbon content, is advantageous in follow-up gasification,
Reduce purification energy consumption and cost.
The purification of step S3 high temperature methods directly rises to maximum temperature compared to conventional high-temperature method of purification, using the side of stepped heating
Formula, use be less than 2750 DEG C (boiling points of silicate mineral) first so that the impurity of part low melting point takes the lead in gasifying and excluded, simultaneously
Help further to discharge the impurity that acid-base method remains, then rise to more than the 2750 DEG C silicate minerals that further gasify,
Stepped heating can avoid, to beginning to heating less than micro crystal graphite using maximum heating temperature eventually, advantageously reducing graphite purification energy
Consumption, temperature is down to room temperature this temperature jump to graphite mechanics or change by highest after can avoiding purification using progressively cooling method
Learn the influence of performance.
Embodiment 2
The present embodiment provides a kind of nuclear graphite preparation method based on micro crystal graphite for raw material, comprises the following steps：
S1. raw ore is handled：By micro crystal graphite crushing raw ore, depth ore grinding then is carried out to micro crystal graphite raw ore, passes through mill
It is -0.074mm level materials that ore deposit, which obtains fineness, is that -0.074mm level material contents account for 90% primary sample and floated to mog
Choosing, using four selected once purging selection flows of one roughing, afterwards drying, magnetic separation, it is 90% microlite to be fixed carbon content
Ink；
Micro crystal graphite raw ore is Shandong pool graphite, wherein moisture 2.4% in the processing of the present embodiment raw ore, volatile matter 2.99%,
The carbon content 78.64% of ash content 18.37%；
S2. acidleach purifies：
S21. microlite ink powder obtained by step S1 is heat-treated at 600~800 DEG C, time 3min；
S22. the mineral after step S2 is heat-treated while hot mix with aqueous slkali, ore pulp liquid-solid ratio 11:1, ultrasound
30min, then carries out alkaline pressure of oxygen leaching under conditions of 105 DEG C of temperature, reaction time 2.5h, and leached mud obtains through washing, after drying
Graphite is soaked to alkali；
S23. alkali obtained by step S3 is soaked into graphite and acid mixes, the acid uses hydrochloric acid or sulfuric acid, ore pulp liquid-solid ratio 11:1,
Ultrasonic 30min, then under conditions of 115 DEG C of temperature, reaction time 2.5h carry out normal pressure acidleach, leached mud distilled water or
Deionized water clean graphite to rinsing solution for it is neutral when precipitate, then filter, dry, obtain graphite powder, fixed carbon content is
99.56%；
The present embodiment aqueous slkali is sodium hydroxide solution, and the concentration of sodium hydroxide solution is 20%；Alkaline pressure of oxygen leaching process
Middle pressure is 0.6~0.8MPa, and the acid is hydrochloric acid or sulfuric acid, concentration of hydrochloric acid 24%, sulfuric acid concentration 98%.
Drying described in the present embodiment step S22 and step S23 is to dry 2~3h in the case where temperature is 80~150 DEG C.
S3. high temperature method purifies：Graphite powder is directly loadable into graphite crucible, is being passed through the purifying of inert gas and protective gas
Using heating up step by step in stove, temperature is risen to 2500~2700 DEG C first, the heat time is 20~30min, is then heated to
2750~3000 DEG C, the heat time is 30~40min, is then progressively cooled to room temperature, is fixed carbon content as 99.998%
High-purity micro crystal graphite；
S4. separating twice：High-purity micro crystal graphite that step S3 is obtained carries out ball milling, screening again, obtains median
D5040 μm of high-purity micro crystal graphite；
S5. isostatic pressing：Step S4 products obtained therefroms are fitted into rubber mold, are then placed in iso-static pressure shaping machine
Row shaping, pressure 200MPa；
S6. it is calcined：By step S5 products obtained therefroms in atmosphere of inert gases, be calcined at 900 DEG C, then by dipping and
It is heavily doped that density is brought up into 1.78g/m3More than；
S7. graphitization：Step S6 products obtained therefroms are inserted in graphitizing furnace, are heated to 1000 DEG C first with 25 DEG C/min,
Then 2800 DEG C are heated to 10 DEG C/min again, keep 10h, then naturally cool to room temperature, finally give based on micro crystal graphite
For the nuclear graphite of raw material.
Embodiment 3
The present embodiment provides a kind of nuclear graphite preparation method based on micro crystal graphite for raw material, comprises the following steps：
S1. raw ore is handled：By micro crystal graphite crushing raw ore, depth ore grinding then is carried out to micro crystal graphite raw ore, passes through mill
It is -0.074mm level materials that ore deposit, which obtains fineness, is that -0.074mm level material contents account for 90% primary sample and floated to mog
Choosing, as shown in figure 1, using four selected once purging selection flows of one roughing, drying, magnetic separation afterwards, being fixed carbon content is
90% micro crystal graphite；
Micro crystal graphite raw ore is Shandong pool graphite, wherein moisture 2.4% in the processing of the present embodiment raw ore, volatile matter 2.99%,
The carbon content 78.64% of ash content 18.37%；
S2. acidleach purifies：
S21. microlite ink powder obtained by step S1 is heat-treated at 800~1000 DEG C, time 3min；
S22. the mineral after step S2 is heat-treated while hot mix with aqueous slkali, ore pulp liquid-solid ratio 12:1, ultrasound
30min, then carries out alkaline pressure of oxygen leaching under conditions of 110 DEG C of temperature, reaction time 3h, and leached mud obtains through washing, after drying
Alkali soaks graphite；
S23. alkali obtained by step S3 is soaked into graphite and acid mixes, the acid uses hydrochloric acid or sulfuric acid, ore pulp liquid-solid ratio 12:1,
Ultrasonic 30min, normal pressure acidleach is then carried out under conditions of 110 DEG C of temperature, reaction time 3h, leached mud distilled water or is gone
Ionized water clean graphite to rinsing solution for it is neutral when precipitate, then filter, dry, obtain graphite powder, fixed carbon content is
99.78%；
The present embodiment aqueous slkali is sodium hydroxide solution, and the concentration of sodium hydroxide solution is 30%；Alkaline pressure of oxygen leaching process
Middle pressure is 0.6~0.8MPa, and the acid is hydrochloric acid or sulfuric acid, concentration of hydrochloric acid 37%, sulfuric acid concentration 98%.
Drying described in the present embodiment step S22 and step S23 is to dry 2~3h in the case where temperature is 80~150 DEG C.
S3. high temperature method purifies：Graphite powder is directly loadable into graphite crucible, is being passed through the purifying of inert gas and protective gas
Using heating up step by step in stove, temperature is risen to 2500~2700 DEG C first, the heat time is 20~30min, is then heated to
2750~3000 DEG C, the heat time is 30~40min, is then progressively cooled to room temperature, is fixed carbon content as 99.998%
High-purity micro crystal graphite；
S4. separating twice：High-purity micro crystal graphite that step S3 is obtained carries out ball milling, screening again, obtains median
D5040 μm of high-purity micro crystal graphite；
S5. isostatic pressing：Step S4 products obtained therefroms are fitted into rubber mold, are then placed in iso-static pressure shaping machine
Row shaping, pressure 300MPa；
S6. it is calcined：By step S5 products obtained therefroms in atmosphere of inert gases, it is calcined at 1000 DEG C, then passes through dipping
Density is brought up into 1.78g/m with heavily doped3More than；
S7. graphitization：Step S6 products obtained therefroms are inserted in graphitizing furnace, are heated to 1000 DEG C first with 30 DEG C/min,
Then 2800 DEG C are heated to 10 DEG C/min again, keep 10h, then naturally cool to room temperature, finally give based on micro crystal graphite
For the nuclear graphite of raw material.
Comparative example 1
This comparative example provides a kind of nuclear graphite materials preparation method, petroleum coke powder is used as raw material, for contrasting cryptocrystalline
Graphite, include following steps：
S1. the parts by weight of petroleum coke powder 30~60 and the parts by weight of asphalt powder 70~45 are put into progress kneading 0.5 in kneading machine
~2h, temperature are 100~200 degree, then crush and obtain particle diameter no more than 40 μm, products obtained therefrom is fitted into rubber mold, then
It is put into iso-static pressure shaping machine and is molded, pressure is 100~300MPa；
S2. step S1 products obtained therefroms are subjected to calcination process, treatment temperature in the atmosphere furnace of halogen or halogenated hydrocarbons is connected with
For 800~1100 DEG C, repeatedly impregnated using pitch and density is brought up into 1.78g/m3More than；
S3. step S2 products obtained therefroms are subjected to graphitization 10h in the graphitizing furnace of the temperature between 2700~3200 DEG C,
It can obtain final nuclear graphite block finished product.
Performance characterization and result
The present invention uses Chenzhou Lu Tang microcrystalline graphite, and its particle is made up of many graphite microcrystals less than 1 μm, from
The diffraction pattern of micro crystal graphite can be seen that these crystallite random orientations in Fig. 2, make micro crystal graphite particle be in isotropism, its structure
Signal is as shown in Figure 3.
The material property of embodiment 1~3 and comparative example is tested, specific as shown in table 1, impurity content such as table
Shown in 2.
Table 1
Table 2
As it can be seen from table 1 the nuclear graphite that the present invention is prepared using aphanitic graphite has very high thermal conductivity, height
Graphitization and low each same tropism ratio, bending strength compared to petroleum coke powder also will height, compared with prior art, the present invention passes through etc. quiet
Pressure can be readily available isotropism than the isotropic graphite for 1.1~1.15, and the green compact thermal diffusion of micro crystal graphite
Rate is significantly larger than the green compact of coke powder, so as to be more beneficial for being calcined.
From table 2 it can be seen that the nuclear graphite impurity that is prepared of the present invention is less than the impurity of comparative example 1, and ash content and
Boron equivalent meets the impurity requirement of nuclear graphite.
Claims (10)
- It is 1. a kind of based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that to comprise the following steps：S1. raw ore is handled：It is 75~80% micro crystal graphite crushing raw ores by fixed carbon content, then micro crystal graphite raw ore is carried out Depth ore grinding, it is -0.074mm level materials to obtain fineness by ore grinding, is that -0.074mm level material contents account for 90% to mog Primary sample carry out flotation, using four selected once purging selection flows of one roughing, drying, magnetic separation, are fixed carbon and contain afterwards Measure as 85~90% micro crystal graphites；S2. acidleach purifies：S21. microlite ink powder obtained by step S1 is heat-treated at 600~800 DEG C, 1~3min of time；S22. the mineral after step S2 is heat-treated while hot mix with aqueous slkali, ore pulp liquid-solid ratio 10~12:1, ultrasound 30min, alkaline pressure of oxygen leaching is then carried out under conditions of 100~110 DEG C of temperature, 2~3h of reaction time, leached mud is through washing, doing Alkali leaching graphite is obtained after dry；S23. alkali obtained by step S3 is soaked into graphite and acid mixes, the acid uses hydrochloric acid or sulfuric acid, ore pulp liquid-solid ratio 10~12:1, Ultrasonic 30min, normal pressure acidleach, leached mud distillation are then carried out under conditions of 100~110 DEG C of temperature, 2~3h of reaction time Water or deionized water clean graphite to rinsing solution for it is neutral when precipitate, then filter, dry, obtain graphite powder, fixed carbon contains Measure as more than 99%；S3. high temperature method purifies：Graphite powder is directly loadable into graphite crucible, in the purifying furnace of inert gas and protective gas is passed through Using heating up step by step, temperature is risen to 2500~2700 DEG C first, the heat time is 20~30min, is then heated to 2750 ~3000 DEG C, the heat time is 30~40min, is then progressively cooled to room temperature, is fixed carbon content as more than 99.993% High-purity micro crystal graphite；S4. separating twice：High-purity micro crystal graphite that step S3 is obtained carries out ball milling, screening again, obtains median D5040μ M high-purity micro crystal graphite；S5. isostatic pressing：Step S4 products obtained therefroms are fitted into rubber mold, be then placed in iso-static pressure shaping machine carry out into Shape, pressure are 100~300MPa；S6. it is calcined：By step S5 products obtained therefroms in atmosphere of inert gases, it is calcined at 800~1000 DEG C, then passes through dipping Density is brought up into more than 1.78g/m3 with heavily doped；S7. graphitization：Step S6 products obtained therefroms are inserted in graphitizing furnace, are heated to 1000 DEG C first with 20~30 DEG C/min, Then 2800 DEG C are heated to 10 DEG C/min again, keep 10h, then naturally cool to room temperature, finally give based on micro crystal graphite For the nuclear graphite of raw material.
- 2. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that in step S1 The micro crystal graphite raw ore is Shandong pool graphite, wherein moisture 2.4%, volatile matter 2.99%, the carbon content 78.64% of ash content 18.37%.
- 3. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that step S22 Described in aqueous slkali be sodium hydroxide solution, the concentration of sodium hydroxide solution is 10 ~ 30%.
- 4. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that step S22 Described in ore pulp liquid-solid ratio be 11:1, temperature is 105 DEG C, reacts 2.5h, during the alkaline pressure of oxygen leaching pressure be 0.6 ~ 0.8MPa。
- 5. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that step S22 It is that 2 ~ 3h is dried in the case where temperature is 80 ~ 150 DEG C with drying described in step S23, ore pulp liquid-solid ratio described in step S23 is 11: 1, temperature is 115 DEG C, reacts 2.5h；The acid is hydrochloric acid or sulfuric acid, and concentration of hydrochloric acid is 2%~37%, sulfuric acid concentration is 7%~ 98%.
- 6. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that in step S5 The pressure is 200MPa.
- 7. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that in step S6 The inert gas is nitrogen.
- 8. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that in step S6 Sintering temperature is 1000 DEG C.
- 9. according to claim 1 based on the nuclear graphite preparation method that micro crystal graphite is raw material, it is characterised in that in step S7 First 1000 DEG C are heated to 25 DEG C/min.
- It is 10. a kind of based on the nuclear graphite that micro crystal graphite is raw material, it is characterised in that the base as described in claim 1~9 any one It is prepared in micro crystal graphite for the nuclear graphite preparation method of raw material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059157A (en) * | 2018-02-13 | 2018-05-22 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method of purification of aphanitic graphite |
| CN108358201A (en) * | 2018-05-22 | 2018-08-03 | 赵文渊 | A kind of graphite purification method |
| CN109735834A (en) * | 2019-01-08 | 2019-05-10 | 黑龙江工业学院 | A kind of copper/micro crystal graphite composite material and preparation method |
| CN111362698A (en) * | 2020-04-28 | 2020-07-03 | 湖南大学 | Novel isotropic nuclear-grade graphite material and preparation method thereof |
| CN111751311A (en) * | 2020-07-03 | 2020-10-09 | 中南大学 | Preparation method of graphite material for oxygen-nitrogen-hydrogen analyzer |
| CN113307265A (en) * | 2021-06-21 | 2021-08-27 | 永安市鼎丰碳素科技有限公司 | High-performance microcrystalline graphite powder material for high-temperature gas cooled reactor and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000090930A (en) * | 1998-09-14 | 2000-03-31 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and manufacture of negative electrode thereof |
| CN101823707A (en) * | 2010-04-28 | 2010-09-08 | 四川广汉士达炭素股份有限公司 | Technical method for producing isostatic pressure graphite |
| CN102502595A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Preparation method of isotropic graphite |
| CN102502603A (en) * | 2011-11-01 | 2012-06-20 | 雅安恒圣高纯石墨科技有限责任公司 | Production process of large isotropic and isostatic high purity graphite with fine particles |
| CN104401982A (en) * | 2014-11-13 | 2015-03-11 | 东莞市翔丰华电池材料有限公司 | Nuclear graphite material preparation method |
-
2017
- 2017-10-31 CN CN201711046252.8A patent/CN107601496B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000090930A (en) * | 1998-09-14 | 2000-03-31 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and manufacture of negative electrode thereof |
| CN101823707A (en) * | 2010-04-28 | 2010-09-08 | 四川广汉士达炭素股份有限公司 | Technical method for producing isostatic pressure graphite |
| CN102502595A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Preparation method of isotropic graphite |
| CN102502603A (en) * | 2011-11-01 | 2012-06-20 | 雅安恒圣高纯石墨科技有限责任公司 | Production process of large isotropic and isostatic high purity graphite with fine particles |
| CN104401982A (en) * | 2014-11-13 | 2015-03-11 | 东莞市翔丰华电池材料有限公司 | Nuclear graphite material preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059157A (en) * | 2018-02-13 | 2018-05-22 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method of purification of aphanitic graphite |
| CN108358201A (en) * | 2018-05-22 | 2018-08-03 | 赵文渊 | A kind of graphite purification method |
| CN109735834A (en) * | 2019-01-08 | 2019-05-10 | 黑龙江工业学院 | A kind of copper/micro crystal graphite composite material and preparation method |
| CN109735834B (en) * | 2019-01-08 | 2020-10-09 | 黑龙江工业学院 | Copper/microcrystalline graphite composite material and preparation method thereof |
| CN111362698A (en) * | 2020-04-28 | 2020-07-03 | 湖南大学 | Novel isotropic nuclear-grade graphite material and preparation method thereof |
| CN111751311A (en) * | 2020-07-03 | 2020-10-09 | 中南大学 | Preparation method of graphite material for oxygen-nitrogen-hydrogen analyzer |
| CN113307265A (en) * | 2021-06-21 | 2021-08-27 | 永安市鼎丰碳素科技有限公司 | High-performance microcrystalline graphite powder material for high-temperature gas cooled reactor and preparation method thereof |
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