CN108529615A - A kind of addition fluoride salt is the graphite purification method of impregnating agent - Google Patents
A kind of addition fluoride salt is the graphite purification method of impregnating agent Download PDFInfo
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Abstract
The present invention relates to a kind of graphite purification methods that addition fluoride salt is impregnating agent, including following production stage：Fluoride salt is added in graphite impregnation agent, is uniformly mixed and obtains being mixed with dipping agent, fluoride salt average grain diameter is 1~2 μm, and the mass ratio of impregnating agent and fluoride salt is 1：0.1~0.3；Then graphite products after primary roasting are subjected to after baking with agent dipping, 3 8MPa of impregnation pressure, 250 450 DEG C of dipping temperature is mixed with dipping；Graphite products are put into graphitizing furnace, furnace core temperature reaches logical nitrogen at 1800~1900 DEG C, when continuing to be warming up to 1900~2000 DEG C, stops nitrogen and is passed through, and be passed through chlorine into stove；Furnace core temperature is more than fluoride salt decomposition generation fluorine gas after 1700 DEG C.The present invention is solved using freon purify in the prior art and be caused to environmental disruption, and progress multi-step gas is needed to be passed through, and technique is cumbersome, problem of high cost.
Description
Technical field：
The present invention relates to graphite preparing technical field, more particularly to a kind of addition fluoride salt is the stone of impregnating agent
Graphite purifying method.
Background technology：
After graphite products complete roasting, some internal magazine elements needs are taken out, and existing purification graphite is all
It is purified into promoting the circulation of qi heat in graphitization, the fusing point and boiling point of most metals halide are all relatively low, especially some higher boilings
Impurity such as boron, vanadium, molybdenum, silicon etc. must could be removed by chlorination and fluorination.In graphitization/purifying, generally in furnace core temperature
Reach a timing to start to be passed through nitrogen, excludes the air in furnace core, then pass to chlorine, when reaching certain temperature to furnace core temperature again
It is passed through freon and chlorine is blown altogether, and then reduce boiling point after so that high-boiling-point impurity is formed compound and be discharged with gas.
The freon that the prior art uses, which can destroy ozone layer, leads to disruption of ecological balance, and needs government's examination ＆ approval to match using unit
Volume, additionally due to freon can only be passed through from the side of stove, gas is by the trend that rises, it is difficult to some corners be avoided to fall
Gas does not reach, and graphite purification is caused to be not thorough.
Invention content：
The purpose of the present invention is in view of the deficiencies of the prior art, provide a kind of graphite adding fluoride salt as impregnating agent
Method of purification enters interiors of products by impregnation pressure by using fluoride salt is added in impregnating agent with impregnating agent so that
In graphite products in being graphitized temperature-rise period, the fluoride salt automatic classifying being mixed in graphite generates fluorine gas to graphite products progress
Purifying is solved using freon purify in the prior art and be caused to environmental disruption, and needs to carry out multi-step gas
It is passed through, technique is cumbersome, problem of high cost.
The technology solution of the present invention is as follows：
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, impregnating agent batch mixing, fluoride salt is added in graphite impregnation agent, obtains being mixed with dipping agent after mixing, should
The average grain diameter of fluoride salt is 1~2 μm, the quality proportioning ranging from 1 of impregnating agent and fluoride salt：0.1~0.3；
Two, it impregnates, the graphite products after primary roasting is impregnated with the hybrid infusion agent being prepared in the step 1,
Then impregnation pressure 3-8MPa, 250-450 DEG C of dipping temperature, and graphite material rate of body weight gain carry out secondary roasting again in 8-20%
Burning processing；
Graphite products obtained by the step 2 are put into graphitizing furnace by three, graphitization/purification process, when furnace core temperature
Degree is passed through nitrogen when reaching 1800~1900 DEG C, when continuing to be warming up to 1900~2000 DEG C, stops nitrogen and is passed through, and start to stove
Inside it is passed through chlorine；Fluoride salt after furnace core temperature is more than 1700 DEG C in graphite products, which decomposes, generates fluorine gas.
As an improvement, the average grain diameter of the fluoride salt in the step 1 is not more than 0.3~0.6 times of impregnated graphite products
3 μm of most probable pore size.
As an improvement, calcination temperature is 850-1000 DEG C, preferably 850-900 DEG C in the step 2；Heating rate is
1-3 DEG C/h, control 50-100 DEG C of the temperature difference in stove.
As an improvement, the fluoride salt is one kind in calcirm-fluoride, sodium fluoride, potassium fluoride and magnesium fluoride.
As an improvement, the quality proportioning of impregnating agent and fluoride salt ranging from 1 in the step 1：0.1~0.2, preferably
1：0.15~0.2；The mixture of impregnating agent and fluoride salt viscosity at 280 DEG C is less than 20cp, and wherein impregnating agent main component is
Selected from coal tar pitch and petroleum asphalt, artificial resin or sugar juice.
As an improvement, impregnation pressure 3-6MPa in the step 2,400-500 DEG C of temperature.
As an improvement, the fluorine gas generates fluoride with impurity element chemical combination in sample, gas is followed to be discharged；It is with boron
Example, boiling point are more than 3500 DEG C, are reacted with fluorine gas, 2B+3F2→2BF3, -127.1 DEG C of the boron fluoride boiling point of generation.
As another improvement, heated up with the speed of 10~30 DEG C/min in the step 3, when furnace core temperature reaches 1820
It is passed through nitrogen at~1900 DEG C, preferably 1850~1900 DEG C and excludes air in furnace core, continues to be warming up to 1920~2000 DEG C, it is excellent
When selecting 1950~2000 DEG C, stop leading to nitrogen and be changed to be passed through chlorine, chlorine is supplied gas 20~25kg/m of unit consumption3。
Wherein, the raw material selection in the present invention：Coke and binder, it is >=98.5% that carbon content is fixed in coke, ash
Dividing≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, and samarium (Sm), europium (Eu), cadmium (Cd) and lithium (Li) are respectively less than 0.5ppm,
Moisture≤0.5%, sulphur content≤0.5%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%.
It is further comprising the steps of before impregnation process that graphite products are prepared using above-mentioned raw material：
(a) material pulverizing, material pulverizing crush so that 5-50 μm of average particle size, the largest particles ranging from 20 μm of -2mm；
(b) dispensing, kneading, by coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 150-400 DEG C of temperature,
The kneading time is in 80-150min；
(c) it is molded, step 3 products obtained therefrom is molded, briquetting pressure 100-250MPa, dwell time 10-80min, it is raw
Base dimensions length is 1000-3200mm, width 500-1500mm, height 300-900mm；
(d) primary roasting, step 4 products obtained therefrom is roasted, and roasts ranging from 800-1100 DEG C of maximum temperature, is risen
Warm rate is 1-5 DEG C/h, and the temperature difference is 50-100 DEG C in stove, and the calcination process time is 65-100 days；
As an improvement, the coke is petroleum coke, pitch coke, mesocarbon microspheres or metallurgical coke, coke raw material needs pre-
Processing, i.e., calcined at a temperature of 1100-1500 DEG C；The binder is that selected from coal tar pitch and petroleum asphalt, artificial resin or sugar are molten
Liquid.
As an improvement, kneading temperature is 200-300 DEG C in the step (b), time 100-140min, preferably 200-
250 DEG C, time 100-120min.
As an improvement, pressure is 120-200Mpa, time 20-60min, preferably, pressure when molding in the step (c)
Power is 120-180MPa, dwell time 40-60min.
As an improvement, calcination temperature is 850-1000 DEG C, preferably 850-900 DEG C respectively in the step (d)；Heating speed
Degree is 1-3 DEG C/h, and controls 50-100 DEG C of the temperature difference in stove.
The present invention is during graphitization/purification process by the way that fluoride salt is added in impregnating agent so that the process of dipping
Middle fluoride salt penetrates into graphite products, and in being graphitized temperature-rise period, the fluoride salt being mixed in graphite can divide graphite products automatically
Solution generates fluorine gas and is purified to graphite products, and one side, which avoids, to be carried out purifying using freon in the prior art and cause
On the other hand the problem of to environmental disruption, passes through to eliminate external equipment in stove due to that can generate fluorine gas inside its own
The process of freon ensure that the effect of graphite purification while simplifying technique.
Further, since fluoride salt early period and impregnating agent are uniformly mixed so that the fluoride salt being distributed in follow-up graphite products
More uniformly, the graphite products various pieces fluoride salt in graphitization, purifying heating up process in stove decomposes the fluorine generated
Gas is also more uniform and can guarantee that there is fluorine gas generation in each corner, improves the effect of purifying, avoids the prior art
In when being passed through gas, cause some corner fluorine gas not reach since it can only be passed through from side and just run up, purifying is not thorough
The case where.
It is passed through molecular weight and boiling point parameter that chlorine and fluorine gas carry out pure treated the nuclear graphite materials metal chloride of core
See below Tables 1 and 2.
Table 1：The molecular weight and boiling point of typical metal chloride
Bibliography：
CRC Handbook of Chemistry and Physics, 75th ed., 1994
PlenumPress Handbook
Table 2：The molecular weight and boiling point of typical metal fluoride
Bibliography：
Merck Index, 11thEdition, 1989
CRC Handbook of Chemistry and Physics, 75th ed., 1994
By Tables 1 and 2 it is found that the present invention is under graphitization processing high temperature, it is passed through after chlorine and fluorine gas in nuclear graphite materials
Metal chloride and metal fluoride boiling point far below the high boron element in graphitization temperature, especially neutron absorption cross-section and
The fluoride boiling point of class boron element substantially reduces, and then can targetedly control the boron equivalent in nuclear graphite materials.
The beneficial effects of the present invention are：
(1) present invention in graphite purification technical process by the way that fluoride salt is added in impregnating agent so that the mistake of dipping
Fluoride salt penetrates into graphite products in journey, and for graphite products in being graphitized temperature-rise period, the fluoride salt being mixed in graphite can be automatic
It decomposes and generates fluorine gas graphite products are purified, one side, which avoids, to be carried out purifying using freon in the prior art and make
On the other hand the problem of pairs of environmental disruption, is led to eliminate external equipment in stove due to that can generate fluorine gas inside its own
The process for crossing freon ensure that the effect of graphite purification while simplifying technique.
(2) since fluoride salt early period and impregnating agent are uniformly mixed in the present invention so that the fluorine being distributed in follow-up graphite products
Also more uniformly, the graphite products various pieces fluoride salt in graphitization/purifying heating up process in stove decomposes production to salt dissolving
Raw fluorine gas is also more uniform and can guarantee that there is fluorine gas generation in each corner, improves the effect of purifying, avoids existing
Have when being passed through gas in technology, cause some corner fluorine gas not reach since it can only be passed through from side and just run up, purifies
Halfway situation.
(3) by the way that the average grain diameter of fluoride salt is arranged most no more than 0.3~0.6 times of impregnated graphite products in the present invention
It can several apertures so that it is converted into gas after the fluorination reactant salt penetrated into graphite products and runs out from graphite products, it will not
The most probable pore size for influencing graphite products will not after becoming larger even if that is, some small holes become larger since fluoride salt is run out of
More than the size of most probable pore size, and it can make some apertures in graphite products more preferably close to most probable pore size, make stone
The aperture of graphite product is more preferably uniform.
(4) present invention in by stretch into the fluoride salt in graphite products by thermal decomposition generate fluorine gas, to graphite products itself into
Row purifying eliminates the external process for being passed through Freon gas, simplifies technique, and the requirement to equipment reduces, cost is reduced.
(5) fluoride salt used in the present invention obtains for the abundant minerals of nature simply, under at low cost.
In conclusion the present invention have it is simple for process, device structure optimization, purified treatment effect is good, environmental-protecting performance height etc.
Advantage is particularly suitable for graphite purification technical field.
Description of the drawings：
Following further describes the present invention with reference to the drawings：
Fig. 1 is the process flow chart for adding the graphite purification method that fluoride salt is impregnating agent；
Specific implementation mode：
1) it is only presently preferred embodiments of the present invention that is as described below, is not defined to the scope of the present invention.
Embodiment one
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain calcirm-fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of calcium：0.1, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and calcirm-fluoride
Mixture viscosity be 14.25；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 16%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt decomposes production after about 2500 DEG C of furnace core temperature
Raw fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of calcirm-fluoride is 1423 DEG C, boiling point is 2500 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：CaF2→Ca↑+F2↑；The fusing point of calcium is 842 DEG C, and boiling point is 1548 DEG C, which can shape in the case of aerobic
At calcium oxide, since graphitization furnace air is caught up with only, so reaction generates calcium simple substance, and therefore higher than 1548 DEG C due to temperature
Gasification discharge.
Embodiment two
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain sodium fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of sodium：0.1, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and sodium fluoride
Mixture viscosity be 10.93cP；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 15.75%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt decomposes production after about 1700 DEG C of furnace core temperature
Raw fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of sodium fluoride is 993 DEG C, boiling point is 1695 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：2NaF→2Na↑+F2↑；The fusing point of calcium is 97.72 DEG C, and boiling point is 883 DEG C, and the decomposition reaction is in the case of aerobic
Sodium oxide molybdena can be formed, since graphitization furnace air is caught up with only, so reaction generates sodium simple substance, and since temperature is higher than 883 DEG C
Therefore gasification discharge.
Embodiment three
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain potassium fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of potassium：0.1, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and potassium fluoride
Mixture viscosity be 12.46cP；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 15.93%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt, which decomposes, behind furnace core temperature about 1500 generates
Fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of potassium fluoride is 858 DEG C, boiling point is 1502 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：2KF→2K↑+F2↑；The fusing point of potassium is 63.25 DEG C, and boiling point is 760 DEG C, decomposition reaction meeting in the case of aerobic
Formed potassium oxide, due to graphitization furnace air caught up with only, so reaction generate potassium simple substance, and due to temperature be higher than 760 DEG C because
This gasification discharge.
Example IV
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain magnesium fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of magnesium：0.1, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and magnesium fluoride
Mixture viscosity be 18.61cP；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 15.86%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt decomposes production after about 2300 DEG C of furnace core temperature
Raw fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of magnesium fluoride is 1261 DEG C, boiling point is 2260 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：MgF2→Mg↑+F2↑；The fusing point of magnesium is 650 DEG C, and boiling point is 1170 DEG C, which can shape in the case of aerobic
At magnesia, since graphitization furnace air is caught up with only, so reaction generates magnesium simple substance, and therefore higher than 1170 DEG C due to temperature
Gasification discharge.
Embodiment five
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain calcirm-fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of calcium：0.2, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and calcirm-fluoride
Mixture viscosity be 18.93cP；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 16.25%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt decomposes production after about 2500 DEG C of furnace core temperature
Raw fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of calcirm-fluoride is 1423 DEG C, boiling point is 2500 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：CaF2→Ca↑+F2↑。
Embodiment six
A kind of addition fluoride salt is the graphite purification method of impregnating agent, including following production stage：
One, raw material select, and select petroleum coke and pitch；Mainly by following raw material and performance indicator：Petroleum coke：Fixed carbon
Content is >=98.5%, and ash content≤0.5%, boron (B), gadolinium (Gd) are respectively less than 0.1ppm, samarium (Sm), europium (Eu), cadmium (Cd) and lithium
(Li) 0.5ppm, moisture≤0.5%, sulphur content≤0.5% are respectively less than；
Pitch：Ash content is≤0.5%, and volatilization is divided into 35-60%, coking value 40-70%, and softening point is 80-200 DEG C,
Quinoline insolubles are 8-25%, toluene insolubles 25-55%；
Ash content is≤0.5% in binder, and volatilization is divided into 35-60%, coking value 40-70%, softening point 80-200
DEG C, quinoline insolubles 8-25%, toluene insolubles 25-55%；
Two, material pulverizing, petroleum coke milling crush so that average particle size is no more than 50 μm；
Three, dispensing, kneading, by petroleum coke 65-80 parts by weight and binder 35-20 parts by weight kneadings, 300 DEG C of temperature is mixed
The time is pinched in 120min；
Four, it is molded, step 3 products obtained therefrom is put into iso-static pressure shaping machine and is molded, briquetting pressure 200MPa, when pressurize
Between be 20min, green compact size length be 2000mm, width 1000mm, height 500mm；
Five, it roasting, step 4 products obtained therefrom is roasted, roasting maximum temperature is 1000 DEG C, and heating rate is 2 DEG C/h,
The temperature difference is no more than 50 DEG C in stove, and the calcination process time is 80 days；
Six, add fluoride salt, fine grain calcirm-fluoride is added in graphite impregnation agent, and is stirred evenly, impregnating agent and fluorine
Change the quality proportioning ranging from 1 of calcium：0.3, under the conditions of this ratio, when temperature is 280 DEG C or so, measure impregnating agent and calcirm-fluoride
Mixture viscosity be 21.46；
Seven, it impregnates, graphite products is impregnated with impregnating agent, impregnation pressure 8MPa, 450 DEG C of dipping temperature, and graphite material
Rate of body weight gain is 16.4%；
Eight, graphitization/purifying, furnace body heating, the sky being passed through when furnace core temperature reaches 1850 DEG C in nitrogen exclusion furnace core
Gas when continuing to be warming up to 1950 DEG C, stops logical nitrogen and is changed to be passed through chlorine；Fluoride salt decomposes production after about 2500 DEG C of furnace core temperature
Raw fluorine gas generates fluoride with impurity element chemical combination in graphite products, and fluoride follows gas to be discharged.
It should be noted that the fusing point of calcirm-fluoride is 1423 DEG C, boiling point is 2500 DEG C, and decomposition at high temperature is anti-
Ying Shiwei：CaF2→Ca↑+F2↑。
2) or less is binder viscosity test tables of data after addition fluoride salt
Table 1：Impregnating agent adds viscosity test table after fluoride salt
1 result of table is shown：Identical in temperature, the Calcium Fluoride Content being added into impregnating agent is higher, binder
Viscosity can be higher；And and mass ratio identical in temperature is also identical, add sodium fluoride after binder viscosity most
It is low, the viscosity highest of binder after magnesium fluoride is added, therefore consider binder viscosity situation and material cost and can obtain
It obtains factors, the final choice calcirm-fluoride such as property to be added in binder, and selects best mass ratio 0.1:1.
It is identical in the fluoride salt type of selection, in the case of the ratio of fluoride salt and binder is also identical, binder it is viscous
Degree declines with the raising of temperature.
Above in association with described in attached drawing being only the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, it is noted that for those skilled in the art, without departing from the structure of the invention, can also make various
Modification and improvement, these should also be considered as protection scope of the present invention, all not interfere with effect and practicability that the present invention is implemented.
Claims (7)
1. a kind of addition fluoride salt is the graphite purification method of impregnating agent, which is characterized in that including following production stage：
One, impregnating agent batch mixing, fluoride salt is added in graphite impregnation agent, obtains being mixed with dipping agent, the fluorination after mixing
The average grain diameter of salt is 1~2 μm, the quality proportioning ranging from 1 of impregnating agent and fluoride salt：0.1~0.3；
Two, it impregnates, the graphite products after primary roasting is impregnated with the hybrid infusion agent being prepared in the step 1, dipping
Then pressure 3-8MPa, 250-450 DEG C of dipping temperature, and graphite material rate of body weight gain carry out calcination process again in 8-20%；
Graphite products obtained by the step 2 are put into graphitizing furnace by three, graphitization/purification process, when furnace core temperature reaches
It is passed through nitrogen when to 1800~1900 DEG C, when continuing to be warming up to 1900~2000 DEG C, stops nitrogen and is passed through, and starts to lead into stove
Enter chlorine；Fluoride salt after furnace core temperature is more than 1700 DEG C in graphite products, which decomposes, generates fluorine gas.
2. a kind of addition fluoride salt as described in claim 1 is the graphite purification method of impregnating agent, it is characterised in that：The step
The average grain diameter of fluoride salt in rapid one is not more than the most probable pore size of 0.3~0.6 times of impregnated graphite products.
3. a kind of addition fluoride salt as described in claim 1 is the graphite purification method of impregnating agent, it is characterised in that：The step
Calcination temperature is 850-1000 DEG C, preferably 850-900 DEG C in rapid two；Heating rate is 1-3 DEG C/h, controls the temperature difference in stove
50-100℃。
4. a kind of addition fluoride salt as described in claim 1 is the graphite purification method of impregnating agent, it is characterised in that：The step
The quality proportioning of impregnating agent and fluoride salt ranging from 1 in rapid one：0.1~0.2, preferably 1：0.15~0.2；Impregnating agent and fluorination
The mixture of salt viscosity at 280 DEG C is less than 20cP.
5. a kind of addition fluoride salt as claimed in claim 4 is the graphite purification method of impregnating agent, it is characterised in that：The fluorine
Salt dissolving is one kind in calcirm-fluoride, sodium fluoride, potassium fluoride and magnesium fluoride.
6. a kind of addition fluoride salt as described in claim 1 is the graphite purification method of impregnating agent, it is characterised in that：The step
Impregnation pressure in rapid two is 3-6MPa, and temperature is 400-500 DEG C.
7. a kind of addition fluoride salt as described in claim 1 is the graphite purification method of impregnating agent, it is characterised in that：The step
It is heated up with the speed of 10~30 DEG C/min in rapid three, when furnace core temperature reaches 1820~1900 DEG C, preferably 1850~1900 DEG C
It is passed through nitrogen, when continuing to be warming up to 1920~2000 DEG C, preferably 1950~2000 DEG C, stops nitrogen and is passed through, and start into stove
It is passed through chlorine, chlorine is supplied gas 20~25kg/m of unit consumption3。
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| CN113061033A (en) * | 2021-03-23 | 2021-07-02 | 辽宁大化国瑞新材料有限公司 | Graphite sphere for high-temperature gas cooled reactor and preparation method thereof |
| CN114890793A (en) * | 2022-05-20 | 2022-08-12 | 中钢天源股份有限公司 | Preparation method of high-purity high-density graphite material |
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