CN106220178A - A kind of heat exchanger graphite material and preparation method thereof - Google Patents
A kind of heat exchanger graphite material and preparation method thereof Download PDFInfo
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- CN106220178A CN106220178A CN201610572845.7A CN201610572845A CN106220178A CN 106220178 A CN106220178 A CN 106220178A CN 201610572845 A CN201610572845 A CN 201610572845A CN 106220178 A CN106220178 A CN 106220178A
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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Abstract
A kind of heat exchanger graphite material, is mainly mixed with is formed by mesophase pitch carbon microspheres, petroleum coke stage material and modified coal tar pitch, and wherein, material of described petroleum coke stage is secondary coking or the acicular petroleum coke of three coking.The preparation method of the present invention: by petroleum coke and modified coal tar pitch slurry, kneading roller roll sheet under vacuum, pulverizes after cooling, and the material after pulverizing carries out batch mixing, standing, isostatic pressing, roasting successively, crushes, and makes petroleum coke stage material；Petroleum coke stage material carries out kneading with mesophase pitch carbon microspheres, and add modified coal tar pitch roller and make sheet, pulverize after cooling, then the material after pulverizing carries out successively mixing, stands, isostatic pressing, roasting carbonization process, graphitization processing, i.e. obtain heat exchanger graphite material.The present invention uses secondary coking or the acicular petroleum coke of three coking first, enhances toughness and the self lubricity of graphite, improves graphite machining efficiency and can improve the thermal conductivity of graphite bulk.
Description
Technical field
The present invention relates to graphite material field, particularly relate to a kind of high compactness, high strength heat exchanger graphite material
And preparation method thereof.
Background technology
Graphite has good anticorrosive, high temperature resistant, the innate advantage such as heat conductivity is good, thermal coefficient of expansion is low, intensity is high, can
Be applied to chemical industry, smelt, oil refining etc. produces in the industry of a large amount of high temperature, corrosivity, strong acid and strong base gas and liquid, especially
In the use of chiller heat exchanger, graphite material has particularly apparent performance advantage.Nowadays heat exchange pipe design
Become increasingly complex, cooling effectiveness is more and more higher, and the requirement for graphite itself also to promote further, not only material require cause
Close property is good, isotropism degree high, intensity is high, heat conductivity is good, the porosity is little, and from the granularity of angle requirement graphite of processing own
Carefully, pliability is good；Especially for slender pipeline, in the processing of multi-angle direction and curved surface pipeline, it is necessary to possess easily processing, do not jump
The characteristics such as angle, not cracking.And at present heat exchanger process close proximity small diameter pipeline time, a lot of graphite bulks but by
The finest and the smoothest in insufficient strength, structure, cause between the course of processing two pipeline, occurring that collapsing the situation such as angle, extruding makes two pipes communicate, and makes
Become to process unsuccessfully；The thermal conductivity of the most general graphite bulk is only 75 ~ 105W/m K.Thus, current heat exchanger is adopted
General graphite material can not meet far away the requirement of current heat exchanger designs.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of high compactness, high intensity
Heat exchanger graphite material and preparation method thereof.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of heat exchanger graphite material, mainly by mesophase pitch carbon microspheres, petroleum coke stage material and modified coal tar pitch mixing
Being prepared from, wherein, material of described petroleum coke stage is secondary coking or the acicular petroleum coke of three coking.
Above-mentioned heat exchanger graphite material, it is preferred that the addition of described modified coal tar pitch is less than raw material gross mass
25%；The mass ratio of described mesophase pitch carbon microspheres and petroleum coke stage material is (9:1) ~ (7:3)；Described acicular petroleum coke
Granularity be 7～10 microns；The granularity of described mesophase pitch carbon microspheres is 7～10 microns.
Above-mentioned heat exchanger graphite material, it is preferred that the softening point temperature of described modified coal tar pitch is 185 ~ 205 DEG C.
As a total inventive concept, the present invention also provides for the preparation side of a kind of above-mentioned heat exchanger graphite material
Method, comprises the following steps:
(1) modified coal tar pitch is made modified coal tar pitch slurry；
(2) petroleum coke and step (1) being prepared, modified coal tar pitch slurry, kneading roller roll sheet under vacuum, cold
Pulverizing the most afterwards, the material after pulverizing carries out batch mixing, standing, isostatic pressing, roasting successively, crushes, and makes secondary coking
The petroleum coke stage expects；
(3) petroleum coke stage material step (2) obtained carries out kneading with mesophase pitch carbon microspheres, and adds modified coal tar pitch roller
Make sheet, pulverize after cooling, then the material after pulverizing carries out successively mixing, stands, isostatic pressing, obtains green compact sample；
(4) green compact sample step (3) obtained carries out roasting carbonization process after standing；
(5) sample that step (4) roasting carbonization processes is carried out graphitization processing, i.e. obtain described heat exchanger graphite material
Material.
Above-mentioned preparation method, it is preferred that the step in step (2) of repetitive operation, makes three Jiao by petroleum coke
The petroleum coke changed.
Above-mentioned preparation method, it is preferred that in secondary coking, the addition of modified coal tar pitch accounts for modified coal tar pitch and oil
The 20% ~ 50% of burnt gross mass；In three cokings, the addition of modified coal tar pitch accounts for modified coal tar pitch and petroleum coke gross mass
20%~50%；
Above-mentioned preparation method, it is preferred that in described step (4), roasting carbonization processing procedure segmentation is carried out, its concrete steps
For: (a) is first warming up to 200～302 DEG C with the heating rate of 5～10 DEG C/h；B () is heated up with the heating rate of 1～3.5 DEG C/h again
To 303～305 DEG C；C () is then warming up to 650～651 DEG C with the heating rate of 1.0～3.0 DEG C/h；D () is again with 0.5～2.0
DEG C/heating rate of h is warming up to 850～852 DEG C；E () is warming up to 1190～1200 DEG C with the heating rate of 1～3 DEG C/h again；
F () is finally down to 40 ~ 50 DEG C with the rate of temperature fall of 5 DEG C/h and is come out of the stove, natural cooling.
Above-mentioned preparation method, it is preferred that in described step (5), graphitization uses medium acheson furnace, burner hearth
Intensification is stable, heating is uniform；Graphited detailed process is: first sample is uniformly heating to 1550～1850 DEG C, insulation 2～
5h, then be uniformly heating to when 2680～2820 DEG C stop power transmission；Wherein in temperature-rise period, when temperature reaches 2100 DEG C ~ 2150 DEG C
Time start to be passed through chlorine, continue to be passed through chlorine 10～12h after stopping power-off, the speed that is passed through of chlorine is 12 ~ 15m3/h；Stopping is sent
Average rate of temperature fall scope after electricity is 2～6 DEG C/h.
Above-mentioned preparation method, it is preferred that in described step (3), the detailed process of isostatic pressing is: first by mixture
Material loads compacting evacuation in mould and processes, and is re-fed in isostatic pressing machine rising to 100 with 10 ~ 15MPa/min rate of pressure rise
～180MPa voltage stabilizing 10～15min, then with 15～20MPa/min pressure release speed pressure releases to 90～120MPa, voltage stabilizing 5～10min；
Finally with 10～15MPa/min pressure release speed pressure releases to chamber pressure.
Above-mentioned preparation method, it is preferred that in described step (2) and described step (3), the concrete technology parameter of kneading
For: all first open wide mixing 1～2h with the temperature of 140～170 DEG C, be subsequently adding modified coal tar pitch slurry, evacuation kneading 1～
2h, then it is warming up to 200 ~ 240 DEG C of vacuum kneading 1 ~ 2h, wherein the rotating speed of kneader controls 80～120r/min.Step (3) is mixed
Volatile matter quality in mixed material after pinching accounts for the 3wt% ~ 15wt% of mixed material quality；It is further preferred that mixed material
Volatile matter quality account for the 5wt% ~ 12wt% of whole mixed material quality.
Above-mentioned preparation method, it is preferred that in described step (1), the preparation process of modified coal tar pitch slurry is: modification dripped
Green grass or young crops with the temperature 24 ~ 48h of 200 ~ 260 DEG C, i.e. obtains described modified coal tar pitch slurry in half hot oil furnace opened wide.Spacious half
In the hot oil furnace of open type, preparation is easy to transpiring moisture and goes out decontamination.
Above-mentioned preparation method, it is preferred that in described step (2) and (3), time of repose is 3～5h；Described step (4)
In, time of repose is 24～48h.
Above-mentioned preparation method, it is preferred that in described step (2), the process of isostatic pressed process refer to first according to 5 ~
The speed of 15MPa/min rises to 160MPa pressurize 10 ~ 30min, the then demoulding, standing 36h；Described roasting process refer to first with 2 ~
5 DEG C/h is warming up to 300 ~ 400 DEG C, is then warming up to 600 ~ 700 DEG C with 1 ~ 2 DEG C/h, then is warming up to 1000 ~ 1100 with 1 ~ 3 DEG C/h
DEG C, natural cooling.
The heat exchanger graphite material of the present invention uses mesophase pitch carbon microspheres to do raw material, and the most only body shrinks,
Aggregate itself also produces contraction, shrinks the biggest, and density increment is the biggest, and after carbonization, compactness wants height, and the porosity is little, it is possible to reduce leaching
Stain and the number of times of roasting, and MCMB makes graphite bulk and the thermal conductivity of material can be made to improve, and strengthens graphite thermal
The heat transfer efficiency of exchanger；Employing acicular petroleum coke is adjuvant, is conducive to nucleus to generate at graphitizing process, improves graphitization
Degree, contributes to the lifting of the thermal conductivity of graphite bulk and the lubricity of graphite, it is simple to improve the retrofit of heat exchanger
Fluency, strengthens the toughness of graphite material, improves the efficiency of machining graphite；Using modified coal tar pitch, it can filled stone oil coke bone
The hole of material, reduces porosity, improves the intensity of petroleum coke aggregate, can also contribute to into as the bonding agent of aggregate simultaneously
Type, is more conducive to the raising of the contraction of bulk, density in roasting process.
The present invention uses the acicular petroleum coke of secondary coking or three coking can improve the true of acicular petroleum coke further
Density, reduces the porosity, particularly can strengthen the compactness of bulk, and the mechanical strength for material is significantly increased；Needle-like
The coking composition of the Colophonium of petroleum coke external sheath, is conducive to the wellability of Colophonium pasting next time, it is possible to strengthen intergranular
Bond strength.
The mesophase pitch carbon microspheres of two kinds of employings of the present invention and the granularity of acicular petroleum coke are relatively thin, form graphite grains
Size also can decline accordingly, dislocation decline makes in neighboring die produce stress decrease, need bigger external carbuncle to make dislocation
Rising in value in adjacent crystal grain, appearance is exactly that the intensity making material increases, and the course of processing is difficult to collapse angle.
Due to the fact that the graphitization goods using MCMB to be main aggregate, owing to overall shrinkage is bigger,
Being particularly easy to crack at firing stage, inventor, by research many times and raw material ratio, is starched by hard pitch
The mobility regulation and control of material, in the case of uniformity disperses the lot of experiments such as the mode of aggregate, repeatedly test the carbonization and stone adapted
Inkization curve, the charging curve comprehensively drawn, it is possible to ensureing carbonization qualification rate, finally find out a whole set of and be suitable for preparation heat friendship
The process conditions of parallel operation graphite material, carbonization qualification rate is more than 85%, and graphited qualification rate is more than 95%.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention uses secondary coking or the acicular petroleum coke of three coking first, can improve grain formation, strengthens graphite
Change degree, further enhances toughness and the self lubricity of graphite, improves graphite machining efficiency and can improve graphite bulk
Thermal conductivity.
(2) the mesophase pitch carbon microspheres of the employing fine grain of the present invention and secondary or three coking acicular petroleum coke conducts
Raw material, body shrinks and self-constriction ability is big, it is possible to be greatly enhanced compactness and the intensity of material.
(3) the raw material valency of present invention use is low is easy to get, and stable in properties, pre-treatment of raw material technique is simple to operation, substantially
Can be prepared by the material of the heat exchanger of graphite that legacy equipment completes excellent performance.
(4) present invention uses mesophase pitch carbon microspheres to be main raw material(s), and acicular petroleum coke is adjuvant, with modified coal tar pitch
For binding agent, use this kind of formula can reduce the circulation technology of carbonization-dipping, in general have only to a roasting carbonization or
Person's double roasting carbonization just can meet original three roastings and the compactness of four roastings, and the process time is from original 8 ~ 10
The moon can foreshorten to 3 ~ 5 months；Not only reduce production cost, improve production efficiency, also save the energy, protect environment.To sum up, this
Bright tradition raw material (forging rear pitch coke and petroleum coke) that overcomes is at roasting and the contraction (body of graphitizing process generation bulk sample
Shrink), the contraction that the most only Colophonium around aggregate produces, the defect that the shrinkage factor of aggregate is the least；During the technique of the present invention
Between can foreshorten to 3 ~ 5 months from traditional 8 ~ 10 months；Not only reduce production cost, improve production efficiency, also save the energy, protect
Retaining ring border.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with preferred embodiment, the present invention is made more comprehensively, describes meticulously,
But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Except there being special instruction, the various reagent used in the present invention, raw material be can commodity commercially or
The product that person can be prepared by known method.
Embodiment 1:
The heat exchanger graphite material of a kind of present invention, it is mainly by mesophase pitch carbon microspheres (hereinafter referred to as: MCMB), pin
Shape petroleum coke and modified coal tar pitch (softening point temperature is 196 DEG C) are mixed with and form；Wherein MCMB and stage material (three coking pins
Shape petroleum coke) mass ratio be 9:1；The addition of modified coal tar pitch is raw material gross weight (modified coal tar pitch+MCMB+ stage expects)
15%。
The preparation method of the heat exchanger graphite material of the present embodiment, comprises the following steps:
(1) modified coal tar pitch (softening point temperature is 196 DEG C) being put into hot oil furnace and heat 36h at 220 DEG C, oil oven lid needs half to open
Open, make modified coal tar pitch slurry；
(2) it is D50=8 micron by acicular petroleum coke comminution by gas stream to granularity, then puts into 40Kg acicular petroleum coke and pinch to vacuum
In conjunction machine, 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding modified coal tar pitch slurry prepared by 30Kg step (1), close machine
Lid, evacuation kneading 1h, then it is warming up to 240 DEG C of kneadings 1h, wherein kneader forward rotational speed controls at 60r/min；
(3) thickener obtained after step (2) kneading is added roll shaft pelleter while hot, by four film-making (roll surface temperatures 210
DEG C, rotating speed 30r/min), by air-cooled for the sheet stock obtained be down to room temperature after be crushed to D50=25 micron, then put will mixing material
Carry out comminution by gas stream to D50=9 micron, put into the rotating speed 200r/min mixing 2h(batch mixer in V-type batch mixer), quiet after blanking
Put 4h, then the powder after standing is loaded isostatic pressing in rubber sleeve, rise to maximum pressure according to the speed of 15MPa/min
Reaching 160MPa, (Baking profile is warming up to 300 DEG C according to 5 DEG C/h, then heats up with 2 DEG C/h for the then demoulding, standing 36h, then roasting
To 700 DEG C, finally it is warming up to 1100 DEG C with 3 DEG C/h, natural cooling), obtain the oil of secondary coking after airflow crash to 8 micron
Defocused；Although the roasting product of preparatory phase material, slow Baking profile is to ensure that Colophonium abundant carbonization in petroleum coke hole,
Improve the carbon yield (Baking profile carbon yield is 76%) of modified coal tar pitch, repeat step (2) and step (3) operation, obtain mixing all
Even three coking acicular petroleum cokes (stage material)；
(4) it is D50=7 micron by mesophase pitch carbon microspheres comminution by gas stream to granularity, then puts into 45Kg mesophase pitch charcoal micro-
Ball and 5Kg stage expect to vacuum kneader, and 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding 8.8Kg step (1) and prepare
Modified coal tar pitch slurry, close cover, evacuation kneading 1h, then be warming up to 240 DEG C of kneadings 1h, kneader forward rotational speed controls
In mixed material after 60r/min, kneading, volatile matter quality accounts for the 8.5% of mixture；
(5) slowly putting in φ 166mm nitrile rubber mould by the mixed material after step (4), counterweight vibrations are compacted, take out very
Empty 20min, puts into equal pressing equipment after glue sealing, first rise to 120MPa, voltage stabilizing with the rate of pressure rise of 15MPa/min
10min；180MPa pressurize 15min is risen to again with the rate of pressure rise of 10MPa/min；Again with 15MPa/min pressure release speed pressure release
To 100MPa, voltage stabilizing 10min；Finally with 5MPa/min pressure release speed pressure release to chamber pressure, obtain regular column type after the demoulding raw
Base sample, is placed in room temperature environment and stands 48h；
(6) green compact sample step (5) obtained loads in stainless steel crucible, fills up the petroleum coke powder that granularity is below 0.5mm,
Ram-jolt, sample distance sidewall of crucible is more than 90mm, and distance crucible top, more than 300mm, proceeds by roasting carbonization process: (a) first with
The heating rate of 5.0 DEG C/h is warming up to 200 DEG C；B () is warming up to 300 DEG C with the heating rate of 2.0 DEG C/h again；C () is then with 1.5
DEG C/heating rate of h is warming up to 650 DEG C；D () is warming up to 850 DEG C with the heating rate of 2 DEG C/h again；E () is again with 1.5 DEG C/h's
Heating rate is warming up to 1200 DEG C；F () is finally cooled to 45 DEG C with the rate of temperature fall of average 5 DEG C/h, obtain carbonization sample, carbonization
Qualification rate more than 85%；
(7) sample after step (6) carbonization is placed in medium acheson furnace it is uniformly heating to 1850 DEG C, be incubated 5h,
It is uniformly heating to 2100 DEG C again, starts with 15m3The speed of/h is passed through chlorine, when temperature rises to 2820 DEG C, stops power transmission, chlorine
Continue conveying 10h, be finally down to 90 DEG C with the rate of temperature fall of 5 DEG C/h and come out of the stove, natural cooling, i.e. can get heat exchanger graphite
Material, graphitization qualification rate reaches more than 95%.
The mean diameter of heat exchanger of graphite material prepared by the present embodiment is 9 μm, and bulk density is 1.95g/cm3, anti-
Compressive Strength is 140.2MPa, and rupture strength is 71.8MPa, and thermal conductivity is 138.1 w/ (m K), resistivity 17.1 μ Ω m, Xiao
Family name's hardness is 60, the porosity 13%, and ash 5 ppm, product qualified rate is more than 89%；Wherein, GB/T 24528-2009 inspection is used
The quasi-bulk density of standard inspection；Compressive resistance is according to GB/T 1431-2009 standard testing；Thermal conductivity is according to GB/T10297-
1998 standard testings；Resistivity is tested according to GB/T 1410-2006；Shore hardness is according to GB/T 4341-2001 standard testing；
The porosity is tested according to GB/T 6155-2008 examination criteria；Ash is according to GB/T 9345.1-2008.Whole graphite thermal exchanges
Device material production cycle is 5 months.Heat exchanger of graphite prepared by the present embodiment, thermal conductivity improves more than 34%, anti-folding and resistance to compression
Improve 40%.
Embodiment 2:
The heat exchanger graphite material of a kind of present invention, mainly by mesophase pitch carbon microspheres (hereinafter referred to as: MCMB), needle-like
Petroleum coke and modified coal tar pitch (softening point temperature is 196 DEG C) are mixed with and form；The wherein needle-like oil of MCMB and three coking
Burnt mass ratio is 8:2；The addition of modified coal tar pitch is gross weight (acicular petroleum cokes of three coking of modified coal tar pitch+MCMB+)
18%。
The preparation method of the heat exchanger graphite material of the present embodiment, comprises the following steps:
(1) modified coal tar pitch (softening point temperature is 196 DEG C) is put into and heats 36h in hot oil furnace at a temperature of 220 DEG C, oil oven lid in
Half opening-wide state, makes modified coal tar pitch slurry；
(2) it is D50=8 micron by acicular petroleum coke comminution by gas stream to granularity, then puts into 40Kg acicular petroleum coke and pinch to vacuum
In conjunction machine, 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding modified coal tar pitch slurry prepared by 30Kg step (1), close machine
Lid, evacuation kneading 1h, then it is warming up to 240 DEG C of kneadings 1h, kneader forward rotational speed controls at 60r/min；
(3) thickener obtained after step (2) kneading is added roll shaft pelleter while hot, by four film-making (roll surface temperatures 210
DEG C, rotating speed 30r/min), by air-cooled for the sheet stock obtained be down to room temperature after be crushed to D50=25 micron, then put will mixing material
Carry out comminution by gas stream to D50=9 micron, put into the rotating speed 200r/min mixing 2h(batch mixer in V-type batch mixer), quiet after blanking
Put 4h, then the powder after standing is loaded isostatic pressing in rubber sleeve, rise to maximum pressure according to the speed of 15MPa/min
Reaching 160MPa, (Baking profile is warming up to 300 DEG C according to 4 DEG C/h, then with 1.5 DEG C/h liter for the then demoulding, standing 36h, then roasting
Temperature, to 700 DEG C, is finally warming up to 1100 DEG C with 3.5 DEG C/h, natural cooling), obtain secondary coking after airflow crash to 8 micron
After petroleum coke；Although the roasting product of preparatory phase material, slow Baking profile is to ensure that Colophonium is abundant in petroleum coke hole
Carbonization, improves the carbon yield (Baking profile carbon yield is 76%) of modified coal tar pitch, repeats step (2) and step (3) operation, obtains
Three coking acicular petroleum cokes (stage material) of mix homogeneously；
(4) it is D50=7 micron by mesophase pitch carbon microspheres comminution by gas stream to granularity, then puts into 40Kg mesophase pitch charcoal micro-
Ball and 10Kg stage expect to vacuum kneader, and 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding 11Kg step (1) and prepare
Modified coal tar pitch slurry, close cover, evacuation kneading 1h, then be warming up to 230 DEG C of kneadings 1h, kneader forward rotational speed controls
At 60r/min；In mixture after kneading, volatile matter quality is 8.4%；
(5) slowly putting in φ 166mm nitrile rubber mould by the mixed material after step (4), counterweight vibrations are compacted, take out very
Empty 20min, puts into equal pressing equipment after glue sealing, first rise to 120MPa, voltage stabilizing with the rate of pressure rise of 15MPa/min
10min；180MPa is risen to again with the rate of pressure rise of 10MPa/min, then with 15MPa/min pressure release speed pressure release to 100MPa,
Voltage stabilizing 10min；Last with 5MPa/min pressure release speed pressure release to chamber pressure, the demoulding, obtain regular column type green compact sample after the demoulding
Product, are placed in room temperature environment and stand 48h；
(6) green compact sample step (5) obtained loads in stainless steel crucible, fills up the petroleum coke powder that granularity is below 0.5mm,
Ram-jolt, sample distance sidewall of crucible is more than 90mm, and distance crucible top, more than 300mm, proceeds by roasting carbonization process: (a) first with
The heating rate of 5.0 DEG C/h is warming up to 200 DEG C；B () is warming up to 300 DEG C with the heating rate of 1.8 DEG C/h again；C () is then with 1.2
DEG C/heating rate of h is warming up to 650 DEG C；D () is warming up to 850 DEG C with the heating rate of 1.8 DEG C/h again；E () is again with 1.5 DEG C/h
Heating rate be warming up to 1200 DEG C；F () is finally cooled to 45 DEG C with the rate of temperature fall of average 5 DEG C/h, obtain carbonization sample, charcoal
Change qualification rate more than 83%；
(7) sample after step (6) carbonization is placed in medium acheson furnace it is uniformly heating to 1850 DEG C, be incubated 5h,
It is uniformly heating to 2100 DEG C again, starts with 15m3The speed of/h is passed through chlorine, when temperature rises to 2820 DEG C, stops power transmission, chlorine
Continue conveying 10h, be finally down to 90 DEG C with the rate of temperature fall of 5 DEG C/h and come out of the stove, natural cooling, i.e. can get heat exchanger graphite
Material, graphitization qualification rate reaches more than 95%.
The mean diameter of heat exchanger of graphite material prepared by the present embodiment is 9 μm, and bulk density is 1.91g/cm3, anti-
Compressive Strength is 133.2MPa, and rupture strength is 68.8MPa, and thermal conductivity is 140.2 w/ (m K), resistivity 16.5 μ Ω m, Xiao
Family name's hardness is 59, the porosity 14%, and ash 5 ppm, product qualified rate is more than 85%；Wherein, GB/T 24528-2009 inspection is used
The quasi-bulk density of standard inspection；Compressive resistance is according to GB/T 1431-2009 standard testing；Thermal conductivity is according to GB/T10297-
1998 standard testings；Resistivity is tested according to GB/T 1410-2006；Shore hardness is according to GB/T 4341-2001 standard testing；
The porosity is tested according to GB/T 6155-2008 examination criteria；Ash is according to GB/T 9345.1-2008.Whole graphite thermal exchanges
Device material production cycle is 5 months.
Embodiment 3:
The heat exchanger graphite material of a kind of present invention, mainly by mesophase pitch carbon microspheres (hereinafter referred to as: MCMB), needle-like
Petroleum coke and modified coal tar pitch (softening point temperature is 196 DEG C) are prepared from；The wherein acicular petroleum coke matter of MCMB and three coking
Amount ratio is 7:3；The addition of modified coal tar pitch is the 20% of gross weight (acicular petroleum cokes of three coking of modified coal tar pitch+MCMB+).
The preparation method for heat exchanger of graphite material of the present embodiment, comprises the following steps:
(1) modified coal tar pitch (softening point temperature is 196 DEG C) is put into and heats 36h in hot oil furnace at a temperature of 220 DEG C, oil oven lid in
Half opening-wide state, makes modified coal tar pitch slurry；
(2) it is D50=8 micron by acicular petroleum coke comminution by gas stream to granularity, then puts into 40Kg acicular petroleum coke and pinch to vacuum
In conjunction machine, 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding modified coal tar pitch slurry prepared by 30Kg step (1), close machine
Lid, evacuation kneading 1h, then it is warming up to 240 DEG C of kneadings 1h, kneader forward rotational speed controls at 60r/min；
(3) thickener obtained after step (2) kneading is added roll shaft pelleter while hot, by four film-making (roll surface temperatures 210
DEG C, rotating speed 30r/min), by air-cooled for the sheet stock obtained be down to room temperature after be crushed to D50=25 micron, then put will mixing material
Carry out comminution by gas stream to D50=9 micron, put into the rotating speed 200r/min mixing 2h(batch mixer in V-type batch mixer), quiet after blanking
Put 4h, then the powder after standing is loaded isostatic pressing in rubber sleeve, rise to maximum pressure according to the speed of 15MPa/min
Reaching 160MPa, (Baking profile is warming up to 300 DEG C according to 4 DEG C/h, then with 2.5 DEG C/h liter for the then demoulding, standing 36h, then roasting
Temperature, to 700 DEG C, is finally warming up to 1100 DEG C with 2.5 DEG C/h, natural cooling), obtain secondary coking after airflow crash to 8 micron
After petroleum coke；Although the roasting product of preparatory phase material, slow Baking profile is to ensure that Colophonium is abundant in petroleum coke hole
Carbonization, improves the carbon yield (Baking profile carbon yield is 76%) of modified coal tar pitch, repeats step (2) and step (3) operation, obtains
Three coking acicular petroleum cokes (stage material) of mix homogeneously；
(4) it is D50=7 micron by mesophase pitch carbon microspheres comminution by gas stream to granularity, then puts into 35Kg mesophase pitch charcoal micro-
Ball and 15Kg acicular petroleum coke stage expect to vacuum kneader, and 120 DEG C are opened wide mixing 1h, stop heating, be subsequently adding
12.5Kg modified coal tar pitch slurry prepared by step (1), close cover, evacuation kneading 1h, then be warming up to 230 DEG C of kneadings 1h,
Kneader forward rotational speed controls at 60r/min；After kneading, in mixed material, volatile matter quality accounts for the 9% of mixed material quality；
(5) slowly putting in φ 166mm nitrile rubber mould by the mixed material after step (4), counterweight vibrations are compacted, take out very
Empty 20min, puts into equal pressing equipment after glue sealing, first rise to 120MPa, voltage stabilizing with the rate of pressure rise of 15MPa/min
10min；180MPa is risen to again with the rate of pressure rise of 10MPa/min, then with 15MPa/min pressure release speed pressure release to 100MPa,
Voltage stabilizing 10min；Last with 5MPa/min pressure release speed pressure release to chamber pressure, the demoulding, obtain regular column type green compact sample after the demoulding
Product, are placed in room temperature environment and stand 48h；
(6) green compact sample step (5) obtained loads in stainless steel crucible, fills up the petroleum coke powder that granularity is below 0.5mm,
Ram-jolt, sample distance sidewall of crucible is more than 90mm, and distance crucible top, more than 300mm, proceeds by roasting carbonization process: (a) first with
The heating rate of 4.0 DEG C/h is warming up to 200 DEG C；B () is warming up to 300 DEG C with the heating rate of 1.5 DEG C/h again；C () is then with 1
DEG C/heating rate of h is warming up to 650 DEG C；D () is warming up to 850 DEG C with the heating rate of 1.5 DEG C/h again；E () is again with 1.5 DEG C/h
Heating rate be warming up to 1200 DEG C；F () is finally cooled to 45 DEG C with the rate of temperature fall of average 5 DEG C/h, obtain carbonization sample, charcoal
Change qualification rate 80%；
(7) sample after step (6) carbonization is placed in medium acheson furnace it is uniformly heating to 1850 DEG C, be incubated 5h,
It is uniformly heating to 2100 DEG C again, starts with 15m3The speed of/h is passed through chlorine, when temperature rises to 2820 DEG C, stops power transmission, chlorine
Continue conveying 10h, be finally down to 90 DEG C with the rate of temperature fall of 5 DEG C/h and come out of the stove, natural cooling, i.e. can get heat exchanger graphite
Material, graphitization qualification rate reaches more than 95%.
The mean diameter of heat exchanger of graphite material prepared by the present embodiment is 9 μm, and bulk density is 1.89g/cm3, anti-
Compressive Strength is 131.2MPa, and rupture strength is 65.0MPa, and thermal conductivity is 135.2 w/ (m K), resistivity 15.1 μ Ω m, Xiao
Family name's hardness is 57, the porosity 15%, and ash 5 ppm, product qualified rate is more than 85%；Wherein, GB/T 24528-2009 inspection is used
The quasi-bulk density of standard inspection；Compressive resistance is according to GB/T 1431-2009 standard testing；Thermal conductivity is according to GB/T10297-
1998 standard testings；Resistivity is tested according to GB/T 1410-2006；Shore hardness is according to GB/T 4341-2001 standard testing；
The porosity is tested according to GB/T 6155-2008 examination criteria；Ash is according to GB/T 9345.1-2008.Whole graphite thermal exchanges
Device material production cycle is 5 months.
Claims (10)
1. a heat exchanger graphite material, it is characterised in that mainly by mesophase pitch carbon microspheres, petroleum coke stage material and
Modified coal tar pitch is mixed with and forms, and wherein, material of described petroleum coke stage is secondary coking or the acicular petroleum coke of three coking.
2. heat exchanger graphite material as claimed in claim 1, it is characterised in that the addition of described modified coal tar pitch does not surpasses
Cross the 25% of raw material gross mass；The mass ratio of described mesophase pitch carbon microspheres and petroleum coke stage material is (9:1) ~ (7:3).
3. heat exchanger graphite material as claimed in claim 1 or 2, it is characterised in that the softening point of described modified coal tar pitch
Temperature is 185 ~ 205 DEG C.
4. the preparation method of the heat exchanger graphite material as described in any one of claims 1 to 3, it is characterised in that
Comprise the following steps:
(1) modified coal tar pitch is made modified coal tar pitch slurry；
(2) modified coal tar pitch slurry petroleum coke and step (1) prepared, kneading roller roll sheet under vacuum, cold
Pulverizing the most afterwards, the material after pulverizing carries out batch mixing, standing, isostatic pressing, roasting successively, crushes, and makes secondary coking stone
The oil coke stage expects；
(3) petroleum coke stage material step (2) obtained carries out kneading with mesophase pitch carbon microspheres, and adds modified coal tar pitch roller
Make sheet, pulverize after cooling, then the material after pulverizing carries out successively mixing, stands, isostatic pressing, obtains green compact sample；
(4) green compact sample step (3) obtained carries out roasting carbonization process after standing；
(5) sample that step (4) roasting carbonization processes is carried out graphitization processing, i.e. obtain described heat exchanger graphite material
Material.
5. preparation method as claimed in claim 4, it is characterised in that the step in step (2) of repetitive operation, by oil
Jiao makes the petroleum coke stage material of three coking.
6. the preparation method as described in claim 4 or 5, it is characterised in that in described step (4), roasting carbonization processing procedure
Segmentation is carried out, and it concretely comprises the following steps: (a) is first warming up to 200～302 DEG C with the heating rate of 5～10 DEG C/h；(b) again with 1～
The heating rate of 3.5 DEG C/h is warming up to 303～305 DEG C；(c) then with the heating rate of 1.0～3.0 DEG C/h be warming up to 650～
651℃；D () is warming up to 850～852 DEG C with the heating rate of 0.5～2.0 DEG C/h again；E () is again with the heating rate of 1～3 DEG C/h
It is warming up to 1190～1200 DEG C；F () is finally down to 40 ~ 50 DEG C with the rate of temperature fall of 5 DEG C/h and is come out of the stove, natural cooling.
7. the preparation method as described in claim 4 or 5, it is characterised in that in described step (5), graphited detailed process
For: first sample is uniformly heating to 1550～1850 DEG C, is incubated 2～5h, then stops when being uniformly heating to 2680～2820 DEG C sending
Electricity；Wherein in temperature-rise period, start to be passed through chlorine when temperature reaches 2100 DEG C ~ 2150 DEG C, continue to be passed through chlorine after stopping power-off
Gas 10～12h, the speed that is passed through of chlorine is 12 ~ 15m3/h；Stopping the average rate of temperature fall scope after power transmission is 2～6 DEG C/h.
8. the preparation method as described in claim 4 or 5, it is characterised in that in described step (3), isostatic pressing concrete
Process is: mixed material first loads compacting evacuation in mould and processes, be re-fed in isostatic pressing machine with 10 ~ 15MPa/min
Rate of pressure rise rises to 100～180MPa voltage stabilizings 10～15min, then with 15～20MPa/min pressure release speed pressure releases to 90～
120MPa, voltage stabilizing 5～10min；Finally with 10～15MPa/min pressure release speed pressure releases to chamber pressure.
9. the preparation method as described in claim 4 or 5, it is characterised in that in described step (2) and described step (3), kneading
Concrete technology parameter be: first open wide mixing 1～2h with the temperature of 140～170 DEG C, be subsequently adding modified coal tar pitch slurry, take out true
Empty also kneading 1～2h, then it is warming up to 200 ~ 240 DEG C of vacuum kneading 1 ~ 2h, wherein the rotating speed of kneader controls 80～120r/
min；
In described step (1), the preparation process of modified coal tar pitch slurry is: by modified coal tar pitch in half hot oil furnace opened wide with 200 ~
Temperature 24 ~ the 48h of 260 DEG C, i.e. obtains described modified coal tar pitch slurry；In described step (2) and (3), time of repose be 3～
5h；In described step (4), time of repose is 24～48h.
10. the preparation method as described in claim 4 or 5, it is characterised in that in described step (2), the process of isostatic pressed process
Refer to first rise to 160MPa pressurize 10 ~ 30min, the then demoulding, standing 36h according to the speed of 5 ~ 15MPa/min；Described roasting
Journey refers to first be warming up to 300 ~ 400 DEG C with 2 ~ 5 DEG C/h, is then warming up to 600 ~ 700 DEG C with 1 ~ 2 DEG C/h, then heats up with 1 ~ 3 DEG C/h
To 1000 ~ 1100 DEG C, natural cooling.
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| CN115340381A (en) * | 2022-09-22 | 2022-11-15 | 东莞市鸿亿导热材料有限公司 | Graphite heat dissipation material and preparation method thereof |
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Denomination of invention: Graphite material for heat exchanger and its preparation method Effective date of registration: 20220928 Granted publication date: 20200110 Pledgee: Ningxiang sub branch of Bank of Changsha Co.,Ltd. Pledgor: HUNAN CHANGYU SCIENCE AND TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2022980016842 |