CN101913593B - Graphite material for producing nanogate carbon and preparation method thereof - Google Patents
Graphite material for producing nanogate carbon and preparation method thereof Download PDFInfo
- Publication number
- CN101913593B CN101913593B CN2010102637393A CN201010263739A CN101913593B CN 101913593 B CN101913593 B CN 101913593B CN 2010102637393 A CN2010102637393 A CN 2010102637393A CN 201010263739 A CN201010263739 A CN 201010263739A CN 101913593 B CN101913593 B CN 101913593B
- Authority
- CN
- China
- Prior art keywords
- time
- product
- petroleum coke
- siccative
- smithing petroleum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a high-volume density fine particle graphite material for producing nanogate carbon and a preparation method thereof. The preparation method mainly comprises the following steps of: crushing, screening and electronically batching; adding tar coke for dry mixing and adding modified asphalt for wet mixing; and vibrating for forming, primarily roasting, primarily impregnating, secondarily roasting, graphitizing and machining to obtain the finished product. On the basis of the prior art, by optimizing the process formula and a key technology according to the use requirement, the preparation method can be used for producing the high-volume density fine particle graphite material for producing nanogate carbon. The graphite material has the characteristics of high purity, high volume density, small particle, low resistivity, uniform and delicate structure, certain mechanical strength and the like.
Description
Technical field:
The present invention relates to a kind of graphite material, particularly, relate to a kind of graphite material and manufacture method thereof that is used for the production nano-sized carbon.
Background technology:
Nano-sized carbon is widely used in fields such as electric heating material, battery production, magnetic pipe recording material, agricultural, Aeronautics and Astronautics because of its special nature, the huge market demand, CN1579932A and CN1579933A have realized the large-batch industrial of nano-sized carbon is produced expeditiously by the pulsed electrode method.The pulsed electrode method is done anode with the high purity graphite material, noble electrode is done negative electrode, the anode graphite electrode obtains energy under the effect of alternating-current pulse electric current, when the energy that obtains when the part carbon atom on the Graphite Electrodes reaches and is enough to overcome graphite carbon interaction between atoms power, swash from electrolytic solution, form nano graphite carbon sol, further nano graphite carbon sol is made carbon powder from nano graphite again, so the graphite anode that is used to prepare nano-sized carbon is a kind of continuous consumption material.This sun level graphite material in order to the preparation nano-sized carbon requires that the purity height is arranged, volume density is big, particle is little, resistivity is low, void content is low, corrosion-resistant, structure and performance uniform and delicate, has characteristics such as certain mechanical strength.
CN101285202A discloses a kind of manufacture method of moulding fine structure graphite anode, this method is broken with high-quality after-smithing petroleum coke and graphite to be aggregate, by pulverizing, sieve into four other superfine powders of base, batching, mixing and make after pinching, roll sheet, secondary abrasive dust, two-sided compression molding method compression moulding, bakes to burn the article, dipping, re-baking, greying.This graphite products uses high quality raw material, adopts super fine powder, fine particle prescription, increases the secondary grinding powder craft, and these have all increased production cost, but the volume density after the compression molding is only greater than 1.55g/cm
3, extrusion forming is one step of key in the graphite technology, and the volume density after the extrusion forming can influence the volume density of graphite finished product largely, and the volume density of this graphite material is only greater than 〉=1.68g/cm
3, volume density does not reach the requirement of high-end product, and its purposes is restricted.
The isostatic pressing formed graphite piece is to have isotropy, high volume density, high strength and structure high added value, the high-end very widely graphite products of industrial use very uniformly, making through operations such as isostatic pressing, roasting, dipping, greying, mechanical workout, purifications of this product by needle coke and pitch, its key process technology is an equal pressing forming technology, and equal pressing forming technology is the plain forming technique of state-of-the-art in the world at present charcoal.
But owing to following reason, the isostatic pressing formed graphite material is not suitable for one large-scale commercial production: 1, produce the used needle coke price height of isostatic pressing formed graphite product, isostatic pressing formed graphite product preparation process complexity, technical difficulty are big, and these all cause the cost of isostatic pressing formed graphite product high.2, the production technology of domestic isostatic pressing formed graphite product is still immature, has only minority producer can produce the undersized product of some low sides, and high-end large size isostatic pressing formed graphite product needs from external import.
At present, the graphite material of producing on the domestic market, or important parameter such as volume density, purity, resistivity do not reach service requirements, or can only carry out the small-scale production of some small sizes, on performance and scale, can't meet the need of market simultaneously.
Given this special proposition the present invention.
Summary of the invention:
An object of the present invention is to provide a kind of graphite material that is used for the production nano-sized carbon, advantages such as this graphite material has the purity height, volume density is big, particle is little, resistivity is low, uniform and delicate structure.
Another object of the present invention has provided a kind of preparation method who is used for the graphite material of production nano-sized carbon.
For realizing first purpose of the present invention, adopt following technical scheme:
The graphite material that is used for the production nano-sized carbon provided by the invention, its volume density reaches 1.74g/cm
3More than, resistivity is below 9 μ Ω m, and purity is greater than 99%.
Preferably, graphite material volume density 〉=1.76g/cm
3Resistivity≤7 μ Ω m; Purity 〉=99.7%.
Preferred, graphite material volume density 〉=1.80g/cm
3Resistivity≤6.7 μ Ω m; Purity 〉=99.8%.
The volume density of graphite material is big more, and purity is high more, and resistivity is low more, electric current and voltage required during the preparation nano-sized carbon is just low more, and the nano carbon particle size of production is just more little, in addition, the dissolution rate of carbon atom can be fast more, and production efficiency is high more, and the work-ing life of graphite material also can be long more.
The graphite material that CN101285202A provides, its volume density 〉=1.68/cm
3Resistivity≤7 μ Ω m; Purity 〉=99%, the volume density of this graphite material is smaller, and electric current and voltage required during the production nano-sized carbon then can be bigger, and the nano carbon particle size of production also can increase, and the nano-sized carbon quality of production is not high.
For realizing second purpose of the present invention, a kind of preparation method who is used for the graphite material of production nano-sized carbon is provided, adopt following technical scheme:
With after-smithing petroleum coke and pitch coke is siccative, modifying asphalt is a cakingagent, by to the fragmentation of siccative, screening, batching, do mix, wet mixing, moulding, bakes to burn the article, dipping, re-baking and greying obtain finished product, described wet mixing is to be to mix under 130 ℃-140 ℃ the condition to pinch with modifying asphalt in temperature with the siccative that obtains after do mixing, obtain thickener, wherein modifying asphalt joins at twice to mix in the siccative and pinches; Described moulding is carried out vibratory compaction with the thickener that obtains, and the volume density of the green compact after the moulding is 1.69g/cm
3More than;
The quality percentage composition that described after-smithing petroleum coke accounts for siccative is 85-90%, and the quality percentage composition that pitch coke accounts for siccative is 10-15%;
The mass percent of described siccative and cakingagent is 75: 25-80: 20;
The granularity of the after-smithing petroleum coke that obtains after fragmentation, screening is less than 1mm, wherein granularity is that the quality percentage composition of the after-smithing petroleum coke of 1.0-0.5mm is that the 20-25% of total after-smithing petroleum coke, the quality percentage composition of after-smithing petroleum coke that granularity is 0.5-0.075mm are the 30-35% of total after-smithing petroleum coke, and granularity is the 40-50% of total after-smithing petroleum coke less than the quality percentage composition of the after-smithing petroleum coke of 0.075mm;
The granularity of described pitch coke is less than 0.075mm.
The present invention is in the process of preparation graphite material, mixing the degree of pinching is vital to the quality of subsequent handling and product, concrete, modifying asphalt joined to mix in the siccative at twice pinch, add a part of modifying asphalt and siccative earlier and cohere, because the amount that adds is few, the stickiness of mixture is lower, under the whipping force effect of equal conditions, can mix at short notice and pinch evenly.After the wet mixing for the first time, the feed particles particle diameter ratio is become greatly more uniformly, its specific surface area is diminished, more remaining modified pitch is added, can be at short notice with siccative and tackiness agent uniform mixing.Add binder modification pitch at twice, both can reduce the time of wet mixing, thickener is mixed pinch evenly, obtain the good thickener of plasticity, obtain the green compact of high volume density through vibratory compaction.Preferably, when adding modifying asphalt, add-on is the 45%-60% of total modifying asphalt quality for the first time, and add-on is the 40%-55% of total modifying asphalt quality for the second time.
Preferably, the quality percentage composition of the after-smithing petroleum coke of 1-0.5mm granularity is 23-24%, and the quality percentage composition of the after-smithing petroleum coke of 0.5-0.075mm granularity is 33-34%, and granularity is 42-44% less than the quality percentage composition of the after-smithing petroleum coke of 0.075mm.
The proportion of macrobead material is big more in the raw material, and then the volume density of finished product is more little, and physical strength reduces, surface irregularity, the proportion of powder is big more in the raw material, then can improve the volume density and the physical strength of graphite material, still, also increased the possibility of product crackle in roasting and the graphitizing process, powder is very strong to the adsorptivity of cakingagent, and powder proportion is big more, and required cakingagent can be many more, the goods void content increases after the roasting, influences the quality of product.
The present invention fully takes into account the granularity of raw material and forms graphite material structure and Effect on Performance, the granularity and the composition of raw material are controlled in the suitable scope, when meeting the requirements of physical and chemical index, taken into account the yield rate of each operation of product, graphite material volume density and the physical strength height produced, flawless.
The granularity of the after-smithing petroleum coke that CN101285202A provides is less than 0.8mm, but its varigrained proportion is different from the present invention, by experiment example 2 as can be known, small-particle material among the present invention and powder can be filled the space of macrobead material more fully, pile up the tightst.
The present invention has added the pitch coke of 10%-15% in preparation process, can improve the physical strength of graphite material, can accelerate product sharp from speed in the electrolytic solution in producing the process of spherical nano-sized carbon again, thus the production efficiency of raising nano-sized carbon.
It is raw material that raw material among the present invention is selected after-smithing petroleum coke and the pitch coke that the source is wide, price is low for use, has reduced production cost, and the price of gained finished product is low, is of value to large-scale industry and promotes.
Described do to mix be meant by prescription and take by weighing after-smithing petroleum coke after the screening and pitch coke as siccative, drops into to mix and pinch pot and do mixedly, and the temperature of siccative is 120-130 ℃, and dried doing time is 35-45 minute.
The total time of described wet mixing is 20-35 minute, and the preferred time is 20-30 minute.
The wet mixing temperature is high more, and pitch is good to the wetting phenomena of siccative, and thickener plasticity improves, and laminate structure is evenly fine and close, and the too high then bituminous of temperature lighting end meeting is run away; The wet mixing time is short, then mixes and pinches inequality, and the wet mixing overlong time then can make the macrobead material be destroyed, and has destroyed original size composition, and bulk specific gravity is reduced, and the volume density of product reduces, the void content height, and intensity reduces; Wet mixing temperature and time of the present invention both can make the mixed material of pinching in the pot mix and pinch evenly, can not destroy original size composition again, after mixed the pinching, had obtained the good thickener of plasticity.
Described moulding is that the thickener that will obtain forms volume density and is preferably greater than 1.72g/cm under the vibrating forming machine effect
3Green compact.
The present invention adopts the vibratory compaction technology, makes green compact obtain higher volume density, and this helps improving the volume density and the mechanical property of finished product, reduces the void content of finished product.Wherein parameters such as the amplitude of vibration processes, frequency are prior art scopes commonly used.
The top temperature of described bakes to burn the article reaches 1050 ℃-1100 ℃, per hour heats up 0.7～1 ℃ when 350～500 ℃ of heating zones, preferably per hour heats up 0.8～0.9 ℃ in the time of 350～500 ℃; In the time of 500～700 ℃, per hour heat up 2-2.5 ℃, preferably in the time of 500～700 ℃, per hour heat up 2.2～2.3 ℃; In the time of 700～850 ℃, per hour heat up 2.5～3 ℃, preferably in the time of 700～850 ℃, per hour heat up 2.6～2.7 ℃.The temperature of bakes to burn the article is when 350～500 ℃ of scopes, volatile matter in row's roasting product, temperature rise rate is very slow, be controlled at per hour between 0.7～1 ℃, hydrocarbon polymer in the roasting product has the comparison adequate time to decompose and polyreaction, improve the coking rate of cakingagent, when 500～700 ℃ of scopes, carbonization at low temperature changes coking into, volatile matter output after modified pitch decomposes further reduces, temperature rise rate is controlled at per hour between 2～2.5 ℃, avoid green compact when diametric(al) is shunk, to crack, guaranteeing that roasting product is indeformable does not ftracture, and when 700～850 ℃ of scopes, continues to have the polycondensation of degradation production and the eliminating of a small amount of volatile matter, the coking degree of goods is more perfect, temperature rise rate is controlled at per hour 2.5～3 ℃, avoids diametric(al) and length direction further to shrink and cracks, and the volume density of roasting product reaches 1.66g/cm behind the bakes to burn the article
3More than.
The present invention controls whole temperature-rise period with the temperature alarming instrument when bakes to burn the article, the temperature range of the roasting curve of assurance temperature alarming instrument and customization has so just been guaranteed the product flawless in 5 ℃, and structure and performance are even.
Described dipping is to carry out under the 1.80MPa-1.95MPa at impregnation pressure, and soaker is medium temperature coal pitch, guarantees that the product rate of body weight gain is more than 15%.
In order to improve the volume density of graphite material, can also realize by the method for repeatedly flooding repeatedly roasting, but this has increased processing step, has improved production cost, has prolonged the production cycle, has reduced production efficiency.
The present invention only needs single-steeping just can reach high volume density, has shortened the production cycle, has improved production efficiency, has reduced production cost.
Described re-baking, roasting time are 144h-168h, and the product top temperature is 800 ℃-850 ℃.
Described greying is the re-baking product to be put into the greying circuit carry out greying, and electric power feeding time is 120h-130h, and the product top temperature reaches 2850 ℃-3000 ℃.
Greying top temperature of the present invention is 2850 ℃-3000 ℃, has promoted the carbon atom arrangement of roasting product to change into the three-dimensional order overlapping from the overlapping of two one-dimensional disorders, has improved the electricity of graphite finished product and conductivity, thermal-shock resistance, chemical stability and the purity of heat.
Compared with prior art, the preparation method's of graphite material provided by the invention beneficial effect is:
It is raw material that the present invention selects after-smithing petroleum coke and the pitch coke that the source is wide, price is low for use, in kneading process, add the tackiness agent modifying asphalt by gradation, make material mix and pinch evenly, can not destroy original size composition again, mix pinch after, obtained density big, evenly, the good thickener of plasticity, and reduced to mix and pinched the time, saved energy consumption, promptly reduced cost, the moulding of the cool material of this thickener after vibration, the green compact flawless, the volume density that obtain reach 1.69g/cm
3More than, be the essential condition that improves the void content of the volume density of finished product and mechanical property, reduction finished product; In roasting process, by rational control heat-up rate, hydrocarbon polymer in the roasting product has the comparison adequate time to decompose and polyreaction, improved the coking rate of cakingagent, improved the physical and chemical performance of goods, guaranteed that roasting product does not indeformablely ftracture, the structure and the performance of whole roasting product are even; Various aspects of performance by the graphite material that obtains after the final greying has approached isostatic pressing formed graphite, its volume density height, flawless, fine particle, physical strength height, when this graphite material is used to prepare nano-sized carbon, dissolution rate in electrolytic solution is fast, thereby improves the production efficiency of nano-sized carbon.
The preparation method of graphite material provided by the invention only needs single-steeping just can reach higher volume density, has shortened the living cycle; And can produce the high performance graphite products of large size heavy industrialization, carry out the mechanical workout cutting according to service requirements then, promptly this preparation method has improved production efficiency, has reduced production cost.
Embodiment:
Embodiment 1
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (85: 15) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 20%, 0.5-0.075mm accounts for 35%, powder accounts for 45% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 20 minutes, and the siccative temperature is 120 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 75: 25, wherein modified pitch adds at twice, add-on is 45% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 10 minutes, and add-on is 55% of total modified pitch amount for the second time, mixing the time of pinching is 15 minutes, and the thickener temperature is 130 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 110 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density is 1.69g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 575h, make product temperature reach 1050 ℃, when 350～500 ℃ of heating zones, per hour heat up 0.7 ℃, in the time of 500～700 ℃, per hour heat up 2 ℃, in the time of 700～850 ℃, per hour heat up 2.5 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, roasting product flawless, volume density 1.66g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 10h warm up time, and preheating temperature is 340 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.80MPa, and the rate of body weight gain of dipping back charcoal piece is 15%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 144h, and the re-baking top temperature is 800 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 120h, and the greying top temperature is controlled at 2850 ℃.Come out of the stove after the machining cutting finally becomes the graphite material that is applicable to the production nano-sized carbon.Graphite finished product flawless, small product size density are 1.78g/cm
3, resistivity is 7 μ Ω m, purity is 99.3%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 2
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (90: 10) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 25%, 0.5-0.075mm accounts for 35%, powder accounts for 40% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 30 minutes, and the siccative temperature is 130 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 80: 20, wherein modified pitch adds at twice, add-on is 50% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 10 minutes, and add-on is 50% of total modified pitch amount for the second time, mixing the time of pinching is 10 minutes, and the thickener temperature is 140 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 120 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density is 1.70g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 569h, the bakes to burn the article top temperature reaches 1100 ℃, when 350～500 ℃ of heating zones, per hour heat up 0.8 ℃, in the time of 500～700 ℃, per hour heat up 2.2 ℃, in the time of 700～850 ℃, per hour heat up 2.6 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, the roasting product flawless, volume density is 1.67g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 12h warm up time, and preheating temperature is 350 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.95MPa, and the rate of body weight gain of dipping back charcoal piece is 16%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 168h, and the product top temperature is 850 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 130h, and the product top temperature is controlled at 3000 ℃.Graphite finished product flawless, its volume density are 1.74g/cm
3More than, resistivity is 9 μ Ω m, purity is 99.5%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 3
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (88: 12) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 25%, 0.5-0.075mm accounts for 30%, powder accounts for 45% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 25 minutes, and the siccative temperature is 125 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 77: 23, wherein modified pitch adds at twice, add-on is 55% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 15 minutes, and add-on is 45% of total modified pitch amount for the second time, mixing the time of pinching is 15 minutes, and the thickener temperature is 135 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 115 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density is 1.69g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 597h, make product temperature reach 1070 ℃, when 350～500 ℃ of heating zones, per hour heat up 0.9 ℃, in the time of 500～700 ℃, per hour heat up 2.3 ℃, in the time of 700～850 ℃, per hour heat up 2.7 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, the roasting product flawless, volume density is 1.65g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 11h warm up time, and preheating temperature is 345 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.85MPa, and the rate of body weight gain of dipping back charcoal piece is 15.5%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 155h, and the re-baking top temperature is 830 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 125h, and the greying top temperature is controlled at 2900 ℃.Graphite finished product flawless, its volume density are 1.76g/cm
3More than, resistivity is 7 μ Ω m, purity is 99.0%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 4
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (88: 12) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 23%, 0.5-0.075mm accounts for 34%, powder accounts for 43% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 25 minutes, and the siccative temperature is 125 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 80: 20, wherein modified pitch adds at twice, add-on is 60% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 15 minutes, and add-on is 40% of total modified pitch amount for the second time, mixing the time of pinching is 20 minutes, and the thickener temperature is 135 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 115 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density is 1.70g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 510h, the bakes to burn the article top temperature reaches 1070 ℃, when 350～500 ℃ of heating zones, per hour heat up 1 ℃, in the time of 500～700 ℃, per hour heat up 2.5 ℃, in the time of 700～850 ℃, per hour heat up 3 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, the roasting product flawless, volume density is 1.63g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 11h warm up time, and preheating temperature is 345 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.85MPa, and the rate of body weight gain of dipping back charcoal piece is 16%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 155h, and the re-baking top temperature is 830 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 125h, and the product top temperature is controlled at 3000 ℃.Graphite finished product flawless, its volume density are 1.80g/cm
3More than, resistivity is 6.8 μ Ω m, purity is 99.7%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 5
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (88: 12) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 24%, 0.5-0.075mm accounts for 34%, powder accounts for 42% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 30 minutes, and the siccative temperature is 130 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 80: 20, wherein modified pitch adds at twice, add-on is 60% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 10 minutes, and add-on is 40% of total modified pitch amount for the second time, mixing the time of pinching is 15 minutes, and the thickener temperature is 140 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 120 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density 1.69g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 578h, the bakes to burn the article top temperature reaches 1100 ℃, makes product temperature reach 1050 ℃, per hour heats up 0.8 ℃ when 350～500 ℃ of heating zones, in the time of 500～700 ℃, per hour heat up 2 ℃, per hour heat up 2.7 ℃ in the time of 700～850 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, and the temperature range that guarantees the temperature alarming instrument is in 5 ℃, roasting product flawless, volume density are 1.63g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 11h warm up time, and preheating temperature is 345 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.85MPa, and the rate of body weight gain of dipping back charcoal piece is 17%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 155h, and the re-baking top temperature is 830 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 125h, and the product top temperature is controlled at 2950 ℃.Greying finished product flawless, its volume density are 1.81g/cm
3More than, resistivity is 7.1 μ Ω m, purity is 99.8%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 6
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (88: 12) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 24%, 0.5-0.075mm accounts for 33%, powder accounts for 43% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 20 minutes, and the siccative temperature is 125 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 80: 20, wherein modified pitch adds at twice, add-on is 60% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 10 minutes, and add-on is 40% of total modified pitch amount for the second time, mixing the time of pinching is 15 minutes, and the thickener temperature is 135 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 115 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, guarantee die mould product flawless, volume density reaches more than the 1.69g/cm3.
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 550h, the bakes to burn the article top temperature reaches 1070 ℃, when 350～500 ℃ of heating zones, per hour heat up 0.8 ℃, in the time of 500～700 ℃, per hour heat up 2.2 ℃, in the time of 700～850 ℃, per hour heat up 2.6 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, the roasting product flawless, volume density is .63g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 11h warm up time, and preheating temperature is 345 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.85MPa, and the rate of body weight gain of dipping back charcoal piece is 15%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 155h, and the re-baking top temperature is 830 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 125h, and the greying top temperature is controlled at 3000 ℃.Graphite finished product flawless, its volume density are 1.81g/cm
3, resistivity is 7.5 μ Ω m, purity is 99.8%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Embodiment 7
After-smithing petroleum coke is made 1-0.5mm, 0.5-0.075mm and three other pellets of level of powder (granularity is less than 0.075mm) after fragmentation, screening, place respectively in three feed bins; Pitch coke is made powder after fragmentation, screening, be stored in the feed bin, by electronic proportioning after-smithing petroleum coke and pitch coke are carried out proportioning by (88: 12) then; Each grade pellet of after-smithing petroleum coke by 1-0.5mm account for 20%, 0.5-0.075mm accounts for 30%, powder accounts for 50% and carries out proportioning.
Above-mentioned compound put into to mix to pinch do mixedly in the pot, dried doing time is 25 minutes, and the siccative temperature is 125 ℃.
Add modifying asphalt in the pot and carry out wet mixing toward mixing to pinch, the mass percent of siccative and modifying asphalt is 80: 20, wherein modified pitch adds at twice, add-on is 60% of total modified pitch amount for the first time, mix with siccative and to pinch, mixing the time of pinching is 10 minutes, and add-on is 40% of total modified pitch amount for the second time, mixing the time of pinching is 15 minutes, and the thickener temperature is 135 ℃.
Thickener is put into dry in the air material operation of the material machine that dries in the air, when treating that the thickener temperature is reduced to 115 ℃, thickener is put into the vibrating forming machine grinding tool carry out vibratory compaction, die mould product flawless, volume density is 1.69g/cm
3
The moulding product are put into ring-form calcining furnace carry out bakes to burn the article, use roasting curve duration to be 550h, the bakes to burn the article top temperature reaches 1050 ℃, when 350～500 ℃ of heating zones, per hour heat up 0.9 ℃, in the time of 500～700 ℃, per hour heat up 2.2 ℃, in the time of 700～850 ℃, per hour heat up 2.6 ℃, whole temperature-rise period is controlled with the temperature alarming instrument, the temperature range that guarantees the temperature alarming instrument in 5 ℃, the product flawless, volume density is 1.63g/cm
3
Roasting product is flooded with coal-tar pitch: earlier roasting product is put into preheating oven and carry out preheating, be 11h warm up time, and preheating temperature is 345 ℃; Product is taken out from preheating oven, put impregnating autoclave into and seal dipping, impregnation pressure is 1.85MPa, and the rate of body weight gain of dipping back charcoal piece is 16.5%.
Pickled product is put into tunnel furnace carries out re-baking, roasting time is 155h, and the re-baking top temperature is 830 ℃.
The re-baking product are put into the greying circuit carry out greying, electric power feeding time is 125h, and the product top temperature is controlled at 3000 ℃.Graphite finished product flawless, its volume density are 1.80g/cm
3More than, resistivity is 6.5 μ Ω m, purity is 99.8%.After the product greying, through the machining cutting, finally become the graphite material that is applicable to the production nano-sized carbon again.
Experimental example 1
This experimental example is that modifying asphalt in the graphite material preparation process of the present invention is added mode to product graphite material performance and mix and pinch the influence of time and analyze, other processing parameter is as embodiment 1, different is that modifying asphalt adds the mode difference, disposable adding is meant required modifying asphalt is once added, it is that mode according to embodiment adds that secondary adds, and the results are shown in Table 1:
As table 1 interpretation of result, by the mode of twice adding modifying asphalt, make to mix and pinch evenly, obtained the good thickener of plasticity, The comprehensive performance is all increased, and shortened to mix and pinched the time, promptly reduced energy consumption.
Experimental example 2
This experimental example is that the influence of raw material, granularity and composition thereof in the graphite material preparation process of the present invention is analyzed, first group of raw material with second group is identical, first group granularity and composition are referring to CN101285202A, second group granularity and composition are referring to the embodiment of the invention 1, other processing parameters the results are shown in Table 2 as embodiment 1.
Table 2
Conclusion: two groups resistivity and folding strength difference are little, but second group volume density is obviously greater than first group, the i.e. granularity of raw material and when forming in adopting the present invention, small-particle material and powder can be filled the space of macrobead material more fully, pile up the tightst.
Claims (5)
1. preparation method who is used for the graphite material of production nano-sized carbon may further comprise the steps:
With after-smithing petroleum coke and pitch coke is siccative, and modifying asphalt is a cakingagent, by to the fragmentation of siccative, screening, batching, do mix, wet mixing, moulding, bakes to burn the article, dipping, re-baking and greying obtain finished product,
Described wet mixing is to be to mix under 130 ℃-140 ℃ the condition to pinch with modifying asphalt in temperature with the siccative that obtains after do mixing, obtain thickener, wherein modifying asphalt joins at twice to mix in the siccative and pinches, for the first time add-on is the 45%-60% of total modifying asphalt quality, and add-on is the 40%-55% of total modifying asphalt quality for the second time;
Described moulding is that the thickener that will obtain carries out vibratory compaction, and the volume density of the green compact after the moulding is 1.69g/cm
3More than;
The top temperature of described bakes to burn the article reaches 1050 ℃-1100 ℃, per hour heats up 0.7～1 ℃ when 350～500 ℃ of heating zones, per hour heats up 2-2.5 ℃ in the time of 500～700 ℃, per hour heats up 2.5～3 ℃ in the time of 700～850 ℃;
The quality percentage composition that described after-smithing petroleum coke accounts for siccative is 85-90%, and the quality percentage composition that pitch coke accounts for siccative is 10-15%;
The mass percent of described siccative and cakingagent is 75: 25-80: 20;
The granularity of the after-smithing petroleum coke that obtains after fragmentation, screening is less than 1mm, wherein granularity is that the quality percentage composition of the after-smithing petroleum coke of 1.0-0.5mm is that the 20-25% of total after-smithing petroleum coke, the quality percentage composition of after-smithing petroleum coke that granularity is 0.5-0.075mm are the 30-35% of total after-smithing petroleum coke, and granularity is the 40-50% of total after-smithing petroleum coke less than the quality percentage composition of the after-smithing petroleum coke of 0.075mm;
The granularity of described pitch coke is less than 0.075mm.
2. according to each described preparation method of claim 1, it is characterized in that the time of described wet mixing is 20-35 minute.
3. preparation method according to claim 1 is characterized in that, described dipping is to carry out under the 1.80MPa-1.95MPa at impregnation pressure, guarantees that the rate of body weight gain of dipping back charcoal piece is more than 15%.
4. preparation method according to claim 1 is characterized in that, the roasting time of described re-baking is 144h-168h, and the top temperature of re-baking is 800 ℃-850 ℃.
5. preparation method according to claim 1 is characterized in that, described graphited electric power feeding time is 120-130h, and graphited top temperature is 2850-3000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102637393A CN101913593B (en) | 2010-08-26 | 2010-08-26 | Graphite material for producing nanogate carbon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102637393A CN101913593B (en) | 2010-08-26 | 2010-08-26 | Graphite material for producing nanogate carbon and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101913593A CN101913593A (en) | 2010-12-15 |
| CN101913593B true CN101913593B (en) | 2011-10-12 |
Family
ID=43321277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102637393A Expired - Fee Related CN101913593B (en) | 2010-08-26 | 2010-08-26 | Graphite material for producing nanogate carbon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101913593B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849729B (en) * | 2012-08-30 | 2014-11-05 | 大同新成新材料股份有限公司 | Heating graphite for heat exchanger and preparation method thereof |
| CN103286850B (en) * | 2012-09-25 | 2014-04-09 | 江苏宏基炭素科技有限公司 | One-time forming method and special mold for graphite crucible |
| CN104016329B (en) * | 2013-03-01 | 2016-04-20 | 江西宁新新材料股份有限公司 | The preparation method of high-density high-strength graphite |
| CN103276408B (en) * | 2013-05-16 | 2015-07-01 | 嘉峪关索通预焙阳极有限公司 | Preparation method of high-quality prebaked anode for 500KA electrolytic cell |
| CN103539109B (en) * | 2013-10-29 | 2015-06-17 | 大同新成新材料股份有限公司 | Graphite material for polysilicon ingot heat preservation thermal field and preparation method thereof |
| CN103882471B (en) * | 2014-03-21 | 2016-10-05 | 天津锦美碳材科技发展有限公司 | A kind of fluorine gas anode material processed and preparation method thereof |
| CN104401975A (en) * | 2014-10-28 | 2015-03-11 | 湖南省长宇新型炭材料有限公司 | Environmental-friendly air gouging carbon electrode and preparation method thereof |
| CN105112942B (en) * | 2015-09-30 | 2017-05-03 | 济南海川投资集团有限公司 | Petroleum coke-manufactured aluminium electrolysis anode formed coke and preparing process thereof |
| CN106602051A (en) * | 2016-12-23 | 2017-04-26 | 山东精工电子科技有限公司 | Preparation method of negative electrode slurry for lithium titanate battery |
| CN107032792B (en) * | 2017-05-16 | 2020-12-11 | 江西宁新新材料股份有限公司 | High-strength high-density graphite material and preparation method thereof |
| CN108101042B (en) * | 2017-12-15 | 2020-02-21 | 大同新成新材料股份有限公司 | Production process of graphite negative electrode material of lithium battery |
| CN108529612B (en) * | 2017-12-19 | 2019-10-25 | 大同新成新材料股份有限公司 | A kind of isostatic pressing formed graphite product and its production method |
| CN110092373A (en) * | 2018-01-29 | 2019-08-06 | 抚顺金利石化炭素有限公司 | A kind of technique producing graphite |
| CN108640681A (en) * | 2018-06-06 | 2018-10-12 | 大同新成新材料股份有限公司 | A kind of preparation method of special graphite carbon material |
| CN109665845A (en) * | 2019-02-12 | 2019-04-23 | 合肥炭素有限责任公司 | A kind of preparation method of composite graphite electrode |
| CN110642248A (en) * | 2019-11-19 | 2020-01-03 | 平顶山市天宝特种材料有限公司 | Production method of fine-structure high-purity graphite with changed molecular arrangement combination |
| CN111081996A (en) * | 2019-11-22 | 2020-04-28 | 大同新成新材料股份有限公司 | Preparation method of silicon-carbon lithium ion negative electrode material |
| CN113816744B (en) * | 2021-08-23 | 2023-02-17 | 吉林炭素有限公司 | Method for determining adjustment direction and addition proportion of graphite electrode coal tar pitch |
| CN113831126A (en) * | 2021-09-17 | 2021-12-24 | 大同新成新材料股份有限公司 | Preparation method of isostatic pressing negative electrode carbon material |
| CN115284422B (en) * | 2022-08-11 | 2023-09-29 | 中钢集团南京新材料研究院有限公司 | Isostatic pressing impregnation method for carbon material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296881A (en) * | 2005-10-28 | 2008-10-29 | 东洋炭素株式会社 | Graphite member for beam-line internal member of ion implantation apparatus |
| CN101357761A (en) * | 2008-09-09 | 2009-02-04 | 河南天利碳素材料有限公司 | High pure graphitic profile and preparation technique thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053200A1 (en) * | 2000-01-17 | 2001-07-26 | Leonid Dmitrievich Bilenko | Method for producing artificial powder graphite |
-
2010
- 2010-08-26 CN CN2010102637393A patent/CN101913593B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296881A (en) * | 2005-10-28 | 2008-10-29 | 东洋炭素株式会社 | Graphite member for beam-line internal member of ion implantation apparatus |
| CN101357761A (en) * | 2008-09-09 | 2009-02-04 | 河南天利碳素材料有限公司 | High pure graphitic profile and preparation technique thereof |
Non-Patent Citations (1)
| Title |
|---|
| 宋永忠等.粘结剂含量对石墨材料电、热传导性能的影响.《新型炭材料》.2002,第17卷(第2期),56-60. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101913593A (en) | 2010-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101913593B (en) | Graphite material for producing nanogate carbon and preparation method thereof | |
| CN102206080B (en) | Graphite material for monocrystalline silicon growth thermal field in solar photovoltaic industry and production method thereof | |
| CN101948675B (en) | Heat accumulation and energy storage graphite material for solar thermal power generation and preparation method thereof | |
| CN103539109B (en) | Graphite material for polysilicon ingot heat preservation thermal field and preparation method thereof | |
| CN107673759A (en) | A kind of preparation method of novel solar generating graphite heat accumulating | |
| CN109133927A (en) | A kind of short flow process of high performance graphite material | |
| CN107602125A (en) | A kind of fine grained, high density, the preparation method of high purity graphite material | |
| CN111170757A (en) | Preparation method of special fine-particle graphite material | |
| CN103553617A (en) | Graphite material for continuous casting mold and preparation method thereof | |
| CN106698414A (en) | Raw material composition and method for preparing special graphite material | |
| CN107732216A (en) | A kind of method that ion cathode material lithium is prepared using C/C composite material granulars | |
| CN108083803B (en) | Preparation method of graphite product formed by die pressing and graphite product | |
| CN107879741B (en) | Preparation method of pure carbon slide bar material of pantograph | |
| CN108610049B (en) | Isotropic graphite material, method for the production thereof and use thereof | |
| CN110127694A (en) | A kind of preparation method of asphalt based active carbon | |
| CN105645386A (en) | Graphite furnace lining used for high purity graphitization furnaces, and preparation method thereof | |
| CN101269980B (en) | Generating method for crassitude carbon nano-tube and carbon nano-fibre in carbon composite refractory material | |
| CN110683845A (en) | Preparation method of carbon graphite product with superfine structure | |
| CN115207349A (en) | Graphite negative electrode material and preparation method and application thereof | |
| CN113213936B (en) | Preparation method of ceramic powder doped modified self-sintered graphite composite material | |
| JP2011093758A (en) | Carbonaceous material | |
| CN113278218B (en) | Conductive composite material with isolation structure and preparation method thereof | |
| CN109755569A (en) | The granulation processing procedure of lithium cell cathode material | |
| CN110416544B (en) | Method for preparing high-capacity artificial graphite cathode material by block semi-closed pore catalytic graphitization | |
| JPH06183835A (en) | Production of preform body for staple fiber-reinforced c/c composite and preform body production by the same method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: DATONG XINCHENG NEW MATERIAL CO., LTD. Free format text: FORMER NAME: DATONG XINCHENG SPECIAL CARBON CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 037002 Shanxi province Datong Xinrong District Garden Tun Xiang Industrial Park Patentee after: DATONG XINCHENG NEW MATERIAL Co.,Ltd. Address before: 037002 Shanxi province Datong Xinrong District Garden Tun Xiang Industrial Park Patentee before: DATONG XINCHENG SPECIAL CARBON Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111012 Termination date: 20210826 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |