CN102849729A - Heating graphite for heat exchanger and preparation method thereof - Google Patents
Heating graphite for heat exchanger and preparation method thereof Download PDFInfo
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- CN102849729A CN102849729A CN2012103158164A CN201210315816A CN102849729A CN 102849729 A CN102849729 A CN 102849729A CN 2012103158164 A CN2012103158164 A CN 2012103158164A CN 201210315816 A CN201210315816 A CN 201210315816A CN 102849729 A CN102849729 A CN 102849729A
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Abstract
The invention specifically relates to heating graphite for a heat exchanger and a preparation method thereof, which belongs to the fields of graphite materials and processing. The preparation method comprises the following steps: fragmentation; screening; batching; kneading; primary roasting; primary dipping; secondary roasting; and graphitization. In the step of graphitization, a heating rate for a graphitization furnace is 13 to 17 DEG C/h when temperature is lower than 1000 DEG C, 23 to 27 DEG C/h when temperature is in a range of 1000 to 1500 DEG C and 33 to 37 DEG C/h when temperature is in a range of 1500 to 2100 DEG C, total graphitization time is 120 to 130 h, and the highest graphitization temperature is 2850 to 3000 DEG C. The preparation method provided by the invention greatly improves physical and chemical performance parameters of a graphite product and enables the graphite product to meet demands of heating graphite for a heat exchanger.
Description
Technical field
The invention belongs to graphite material and manufacture field, be specifically related to a kind of heat exchanger with heating graphite and preparation method thereof.
Background technology
In recent years along with the fast development in heat exchanger market, people significantly improve the requirement of making the interchanger material.For the heat transfer problem that solves strong corrosive media, improve its heat transfer coefficient, and adapt to heat exchange and energy-conservation needs under the high temperature and high pressure condition, the interchanger that people make type material begins to note.General interchanger is all made some with metallic substance and has been begun for the anti-corrosion interchanger of making non-metallic material, such as graphite heat exchanger.Currently available products is being used for there are the deficiencies such as corrosion-resistant, the easy fouling of heat-transfer surface, tension and bending strength are low when heat exchanger uses, production and use cost have greatly been increased, be unfavorable for the sale of this series products and popularize, developing target market there is inhibition, has restricted the update of product.
CN 201010263217.3 discloses a kind of graphite material for solar energy thermal-power-generating heat build-up accumulation of energy and preparation method thereof, and the performance perameter of described graphite material satisfies: volume density 〉=1.75g/cm
3, resistivity≤7.5 μ Ω m, ash≤0.2% folding strength 〉=18.5Mpa, Young's modulus≤8.8Gpa, thermal expansivity≤2.0x10
-6/ ℃
-1Graphite material of the present invention has the thermal capacity height, and thermal conductivity is high, long service life, low cost and other advantages.Its preparation method is: with raw material by screening, batching, kneading, the material that dries in the air, vibratory compaction, again through after roasting, dipping, re-baking, greying, the mechanical workout the heat-storing material of focusing solar energy generating.
CN201110115307.2 discloses a kind of photovoltaic industry monocrystalline silicon growing thermal field graphite material, and in the raw material of described graphite material, aggregate is after-smithing petroleum coke, the true density 〉=2.1g/cm of described after-smithing petroleum coke
3, ash content≤0.3%, binding agent are mid-temperature pitch, the softening temperature of described mid-temperature pitch is 83 ~ 86 ℃, coking value 〉=49%.Volume density 〉=the 1.80g/cm of described graphite material
3, resistivity≤7.0 μ Ω m, ultimate compression strength 〉=38Mpa, folding strength 〉=18Mpa, void content≤14%, ash content≤0.2%, thermal expansivity≤2*10
-6/ ℃.The preparation method of this graphite material may further comprise the steps: the fragmentation of raw material, screening, batching, kneading, moulding, bakes to burn the article, single-steeping, re-baking, double-steeping, three roastings and greying obtain finished product.
Although the graphite material that above-mentioned patent provides has higher volume density and intensity, lower resistivity, its thermal conductivity is lower, and the over-all properties parameter of the graphite material that above-mentioned patent provides but can not satisfy heat exchanger with the demand of heating graphite.
In view of this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of heat exchanger preparation method of heating graphite, described preparation method has greatly improved the physicochemical property parameter of the finished product by improving technique, can satisfy the heat exchanger demand that heats graphite.
Another object of the present invention is to provide a kind of heat exchanger of above-mentioned preparation method's preparation that adopts with heating graphite.
In order to realize purpose of the present invention, the following technical scheme of special employing:
A kind of heat exchanger preparation method of heating graphite, comprise that fragmentation, screening, batching, kneading, moulding, bakes to burn the article, single-steeping, re-baking and greying obtain finished product, described graphite turns to: below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 13-17 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 23-27 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 33-37 ℃/time; Described graphited total time is 120-130h, and described graphited top temperature is 2850-3000 ℃.
Among the preparation technology of graphite, graphited heating curve directly affects the degree of graphitization of charcoal piece and the physicochemical property of graphite product, the present invention is take after-smithing petroleum coke and pitch coke as compound, the graphitization temperature of after-smithing petroleum coke and pitch coke is interval different, and the best greying temperature rise rate of after-smithing petroleum coke and pitch coke is also different, the contriver is through repeatedly experiment, finally determine below 1000 ℃ the time, adopt slower speed to heat up, after this, faster speed with 23-27 ℃/h between 1000-1500 ℃ heats up, further improving speed between 1500-2100 ℃ heats up, greying temperature rise rate of the present invention is taken into account the graphitizing process of after-smithing petroleum coke and pitch coke, makes the greying conversion of the two tend to consistent as far as possible, and greying is effective.In addition, among the graphite preparation technology of the present invention, only need carry out re-baking gets final product greying, and operational path is simple, has greatly reduced production cost, and the graphite material for preparing under the condition of simplifying operational path still has very excellent over-all properties.
Preferably, described graphite turns to: below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 15 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 25 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 35 ℃/time.
In the described graphitizing furnace, the spacing of greying graphite is 100-120mm, and filler is pure graphitized coke, and the granularity of described pure graphitized coke is 10-35mm.
The contriver finds after deliberation, different greying fillers has considerable influence to physical strength, heat conductivility and the conductivity of greying product, as can improving the physical strength of graphite products take carbon black as filler, but heat conductivility and the electroconductibility of graphite products there is negative impact.The present invention selects graphitized coke take the 10-35mm granularity as filler, and graphite products has higher ultimate compression strength, folding strength and thermal conductivity and lower resistivity after greying.
Described batching is: the weight ratio of compound and mid-temperature pitch is 78-80:20-22, and described compound is after-smithing petroleum coke and pitch coke, and the weight ratio of described after-smithing petroleum coke and pitch coke is 65-70:30-35; Preferably, the weight ratio of described compound and mid-temperature pitch is 80:20, and the weight ratio of described after-smithing petroleum coke and pitch coke is 70:30.
The particle size range of described after-smithing petroleum coke and content are:
0.7mm＜particle diameter≤0.5mm 10%-25%,
0.5mm＜particle diameter≤0.335mm 25%-30%,
0.335mm＜particle diameter≤0.075mm 20%-25%,
Particle diameter＜0.075mm 30%-40%;
Particle size range and the content of described after-smithing petroleum coke are preferably:
0.7mm＜particle diameter≤0.5mm 15%-20%,
0.5mm＜particle diameter≤0.335mm 27%-29%,
0.335mm＜particle diameter≤0.075mm 20%-23%,
Particle diameter＜0.075mm 33%-37%;
The granularity of described pitch coke is less than 0.075mm.
The present invention considers different components and consumption, the size of each component is to volume density, resistivity, intensity, thermal expansivity, the various impacts of thermal conductivity and void content, large percentage such as after-smithing petroleum coke in the compound, be conducive to improve the volume density of finished product, but pitch coke and mid-temperature pitch at graphitization process easily in greying, the particle size range of compound and content influence particle packing mode and then to affect the volume of graphite product close, void content, thermal conductivity and resistivity etc., the contriver is through repeatedly research, prepare burden according to above-mentioned prescription, finally obtained to have the graphite product of desirable over-all properties.
Described bakes to burn the article is: the temperature of igniting is 220-230 ℃, the top temperature of bakes to burn the article is 1100-1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.6-2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8-1.1 ℃/h, 500-850 ℃ temperature rise rate is 2.0-2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5-3.5 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.
Described single-steeping is: the graphite behind the bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, and the vacuum tightness in the impregnating autoclave is-0.086Mpa that injection soaker floods 5-7h under 1.85-2.0Mpa pressure.
Preferably, described single-steeping is: the graphite behind the bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, and the vacuum tightness in the impregnating autoclave is-0.086Mpa to inject soaker, first under 1.85-1.90Mpa pressure, flood 2-3h, be forced into again under the 1.90-2.0Mpa and flood 2-3h.
When dipping, first the carbon element product of need dipping vacuumized first, the purpose that vacuumizes is the gas of discharging in the carbon element product open pores that needs dipping, is beneficial to the infiltration of impregnating pitch.After adding impregnating pitch, under the effect of pressure, impregnating pitch is than going in the hole that is easier to be penetrated into the carbon element product that need dipping, thus the assurance rate of body weight gain.The present invention is in the process of single-steeping, under certain original pressure, flood first, the quinoline that contains in the soaker in the steeping process not fusant can form thin film on the pickled product surface of porous, hinder soaker to the infiltration of porous pickled product, affected the effect of dipping, the present invention adopts the mode of secondary pressurized in the process of dipping, thereby has guaranteed dipping effect.
The characteristic of impregnating pitch has important impact to dipping effect, is mainly manifested on the viscosity, quinoline insolubles content, coking value of pitch.Coking value is higher, the volume density of product and physical strength are larger after the roasting, and coking value increases with the softening temperature rising, therefore adopt the higher impregnating pitch of softening temperature as cakingagent, be conducive to improve volume density and the physical strength of graphite material, but the impregnating pitch softening temperature is higher, and relative viscosity is just larger, is difficult to be penetrated in the hole of pickled product go.Asphalt viscosity was affected by nature both, just was inversely proportional to Heating temperature again.For improving dipping effect, among the present invention, described soaker is impregnating pitch, in the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Described re-baking is: the temperature of igniting is 220-230 ℃, the top temperature of re-baking is 1100-1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.6-2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8-1.1 ℃/h, 500-850 ℃ temperature rise rate is 2.0-2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5-3.5 ℃/h; Filler granularity around the re-baking product is 2-6mm; Distance between re-baking product and the wall with flues is not less than 150mm.
The purpose of roasting is to make the binder pitch charing, forms the coke grid between particles of aggregates, and varigrained aggregate is bonded to an integral body securely.The small-particle prescription is when the preparation graphite material, the chance that occurs crackle in follow-up roasting and graphitizing process is many, yield rate may be on the low side, the present invention according to the composition of raw material and content with and granularity by optimizing and the factors such as heating curve when improving roasting, the duration of heat, improved the coking rate of binding agent, overcome the low problem of appearance crackle, yield rate that small-particle brings, to guarantee product overall target and yield rate.Identical roasting curve is adopted in three roastings of the present invention, it is low-temperature ignition, temperature rise rate below 400 ℃ is 1.6-2.0 ℃/h, lightweight fugitive constituent in the roasting product is discharged with slower speed volatilization, the suffered pressure of roasting product inside is less, balance comparatively, avoided the generation of crackle in the temperature-rise period, and light component there is the sufficient time to discharge roasting product; Polycondensation strengthens in the 400-500 ℃ of roasting product, coke begins to form, temperature rise rate with 0.8-1.1 ℃/h heats up, be conducive to improve the coking rate of binding agent, carbonization at low temperature changes coking into, and 500-850 ℃ of polycondensation continues to occur, the further coking of goods, slower temperature rise rate with 2.0-2.3 ℃/h heats up, and is conducive to improve volume density and the intensity of roasting product, and avoids that roasting product cracks when shrinking in the process of polycondensation; Temperature rise rate more than 850 ℃ is 2.5-3.5 ℃/h, the further densification of the weave construction of roasting product.
Heat exchanger according to foregoing preparation method's preparation with the physicochemical property parameter that heats graphite is: resistivity≤8.0 μ Ω m, folding strength 〉=13Mpa, ultimate compression strength 〉=32Mpa, volume density 〉=1.75g/cm
3, thermal expansivity≤3.2*10
-6/ ℃, thermal conductivity 〉=110W/mk, void content≤20%.
Preferably, described heat exchanger with the physicochemical property parameter of heating graphite is: described resistivity≤7.0 μ Ω m, folding strength 〉=17Mpa, ultimate compression strength 〉=39Mpa, volume density 〉=1.80g/cm
3, thermal expansivity≤3.0*10
-6/ ℃, thermal conductivity 〉=120W/mk, void content≤15%.
Compared with prior art, beneficial effect of the present invention is:
The present invention is by optimizing and improvement preparation technology, heating curve and impregnation method when particularly passing through optimization and improving Graphitizing Furnace Rise Temprature Process Curve, roasting, the graphite material of preparation has extraordinary over-all properties, can be used for heat exchanger with heating graphite, but raw material sources are wide, price is low, preparation technology is relatively simple, and technical difficulty is low, and production cost is low.
Embodiment
The specific embodiment of the present invention only makes further explanation content of the present invention, not to Composition of contents restriction of the present invention.Raw material of the present invention is marketable material, and the mechanical means that adopts also is the equipment that this area is known altogether.
Embodiment 1
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 10%, 0.5mm＜particle diameter≤0.335mm accounts for 30%, 0.335mm＜particle diameter≤0.075mm accounts for 20%, particle diameter＜0.075mm accounts for four other pellets of level of 40%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 65:35.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 80:20.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 220 ℃, the top temperature of bakes to burn the article is 1100 ℃, wherein the temperature rise rate below 400 ℃ is 1.6 ℃/h, 400-500 ℃ temperature rise rate is 1.1 ℃/h, 500-850 ℃ temperature rise rate is 2.0 ℃/h, and the temperature rise rate more than 850 ℃ is 3.5 ℃/h; Filler granularity around the bakes to burn the article product is 6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 340 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa that the injection impregnating pitch floods 7h under 1.85Mpa pressure.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 220 ℃, the top temperature of roasting is 1100 ℃, wherein the temperature rise rate below 400 ℃ is 1.6 ℃/h, 400-500 ℃ temperature rise rate is 1.1 ℃/h, 500-850 ℃ temperature rise rate is 2.0 ℃/h, and the temperature rise rate more than 850 ℃ is 3.5 ℃/h; Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 13 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 27 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 33 ℃/time; Described graphited top temperature is 2850 ℃, and described graphited total time is 120h.The resistivity of graphite finished product flawless, product is 8.0 μ Ω m, and folding strength is 13Mpa, and ultimate compression strength is 32Mpa, and volume density is 1.75g/cm
3, thermal expansivity is 3.2*10
-6/ ℃, thermal conductivity is 110W/mk, void content is 20%.
Embodiment 2
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 20%, 0.5mm＜particle diameter≤0.335mm accounts for 25%, 0.335mm＜particle diameter≤0.075mm accounts for 25%, particle diameter＜0.075mm accounts for four other pellets of level of 30%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 70:30.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 78:22.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 230 ℃, the top temperature of bakes to burn the article is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8 ℃/h, 500-850 ℃ temperature rise rate is 2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 380 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa that the injection impregnating pitch floods 5h under 2.0Mpa pressure.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 230 ℃, the top temperature of roasting is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8 ℃/h, 500-850 ℃ temperature rise rate is 2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5 ℃/h; Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 17 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 23 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 37 ℃/time; Described graphited top temperature is 3000 ℃, and described graphited total time is 130h.The resistivity of graphite finished product flawless, product is 7.9 μ Ω m, and folding strength is 13Mpa, and ultimate compression strength is 33Mpa, and volume density is 1.78g/cm
3, thermal expansivity is 3.2*10
-6/ ℃, thermal conductivity is 110W/mk, void content is 20%.
Embodiment 3
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 25%, 0.5mm＜particle diameter≤0.335mm accounts for 25%, 0.335mm＜particle diameter≤0.075mm accounts for 20%, particle diameter＜0.075mm accounts for four other pellets of level of 30%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 67:33.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 78:22.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 230 ℃, the top temperature of bakes to burn the article is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8 ℃/h, 500-850 ℃ temperature rise rate is 2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 380 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa that the injection impregnating pitch floods 5h under 2.0Mpa pressure.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 220 ℃, the top temperature of roasting is 1100 ℃, wherein the temperature rise rate below 400 ℃ is 1.6 ℃/h, 400-500 ℃ temperature rise rate is 1.1 ℃/h, 500-850 ℃ temperature rise rate is 2.0 ℃/h, and the temperature rise rate more than 850 ℃ is 3.5 ℃/h.Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 13 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 23 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 37 ℃/time; Described graphited top temperature is 3000 ℃, and described graphited total time is 125h.The resistivity of graphite finished product flawless, product is 1.8 μ Ω m, and folding strength is 15Mpa, and ultimate compression strength is 34Mpa, and volume density is 1.77g/cm
3, thermal expansivity is 3.2*10
-6/ ℃, thermal conductivity is 110W/mk, void content is 18%.
Embodiment 4
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 15%, 0.5mm＜particle diameter≤0.335mm accounts for 29%, 0.335mm＜particle diameter≤0.075mm accounts for 23%, particle diameter＜0.075mm accounts for four other pellets of level of 33%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 70:30.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 80:20.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 230 ℃, the top temperature of bakes to burn the article is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 380 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa, injects impregnating pitch, floods 2h under 1.85Mpa pressure first, is forced under the 1.90Mpa pressure again and floods 3h.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 230 ℃, the top temperature of roasting is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 15 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 25 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 35 ℃/time; Described graphited top temperature is 3000 ℃, and described graphited total time is 125h.The resistivity of graphite finished product flawless, product is 7.0 μ Ω m, and folding strength is 20Mpa, and ultimate compression strength is 39Mpa, and volume density is 1.80g/cm
3, thermal expansivity is 3.0*10
-6/ ℃, thermal conductivity is 125W/mk, void content is 15%.
Embodiment 5
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 20%, 0.5mm＜particle diameter≤0.335mm accounts for 27%, 0.335mm＜particle diameter≤0.075mm accounts for 20%, particle diameter＜0.075mm accounts for four other pellets of level of 33%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 70:30.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 80:20.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 230 ℃, the top temperature of bakes to burn the article is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 380 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa, injects impregnating pitch, floods 3h under 1.90Mpa pressure first, is forced under the 2.0Mpa pressure again and floods 2h.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 230 ℃, the top temperature of roasting is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 15 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 25 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 35 ℃/time; Described graphited top temperature is 3000 ℃, and described graphited total time is 125h.The resistivity of graphite finished product flawless, product is 6.7 μ Ω m, and folding strength is 17Mpa, and ultimate compression strength is 42Mpa, and volume density is 1.80g/cm
3, thermal expansivity is 3.0*10
-6/ ℃, thermal conductivity is 120W/mk, void content is 13%.
Embodiment 6
Batching: with after-smithing petroleum coke make after broken, screening that 0.7mm＜particle diameter≤0.5mm accounts for 16%, 0.5mm＜particle diameter≤0.335mm accounts for 27%, 0.335mm＜particle diameter≤0.075mm accounts for 20%, particle diameter＜0.075mm accounts for four other pellets of level of 37%, place respectively in four feed bins; The granularity of pitch coke after fragmentation is less than 0.075mm.Wherein the weight ratio of after-smithing petroleum coke and pitch coke is 70:30.
The above-mentioned compound for preparing put in the kneading pot be dry mixed, after mixing, add mid-temperature pitch and carry out wet mixing, wherein the compound that forms of after-smithing petroleum coke and pitch coke and with the weight ratio of mid-temperature pitch be 80:20.Thickener after the wet mixing is put into the material machine that dries in the air dry in the air material, vibratory compaction.
Products formed is put into ring-form calcining furnace carry out bakes to burn the article, described bakes to burn the article is: the temperature of igniting is 230 ℃, the top temperature of bakes to burn the article is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.Whole temperature-rise period is controlled with the temperature alarming instrument, guarantees the temperature range of temperature alarming instrument in 5 ℃, the roasting product flawless.
Enter impregnating autoclave after charcoal piece behind the bakes to burn the article is preheating to 380 ℃, the vacuum tightness in the impregnating autoclave be-0.086Mpa, injects impregnating pitch, floods 3h under 1.85Mpa pressure first, is forced under the 1.90Mpa pressure again and floods 2h.In the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
Then carry out re-baking: the temperature of igniting is 230 ℃, the top temperature of roasting is 1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.8 ℃/h, 400-500 ℃ temperature rise rate is 1.0 ℃/h, 500-850 ℃ temperature rise rate is 2.2 ℃/h, and the temperature rise rate more than 850 ℃ is 3.0 ℃/h; Filler granularity around the roasting product is 2-6mm; Distance between roasting product and the wall with flues is not less than 150mm.
Charcoal piece behind the re-baking is put into the greying circuit carry out greying, below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 15 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 25 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 35 ℃/time; Described graphited top temperature is 3000 ℃, and described graphited total time is 125h.The resistivity of graphite finished product flawless, product is 6.9 μ Ω m, and folding strength is 25Mpa, and ultimate compression strength is 44Mpa, and volume density is 1.83g/cm
3, thermal expansivity is 3.0*10
-6/ ℃, thermal conductivity is 130W/mk, void content is 15%.
Experimental example 1
This experimental example has compared different preparation methods to the impact of graphite products performance perameter.
First group is the graphite material according to the method preparation of the embodiment 4 of CN201110115307.2, and adopts the general method in this area to measure its physicochemical property parameter;
Second group is the graphite material according to the method preparation of the embodiment 8 of CN201010263217.3, and adopts the general method in this area to measure its physicochemical property parameter;
The 3rd group is the graphite material according to the method preparation of the embodiment 7 of CN201010263739.3, and adopts the general method in this area to measure its physicochemical property parameter.
The graphite material that conclusion: CN201110115307.2, CN201010263217.3, CN201010263739.3 provide is the product that obtains through three roastings and greying, operational path is comparatively complicated, production cost is high, and indivedual physical and chemical parameters are lower, lower or physical strength is lower such as thermal conductivity, the over-all properties of the graphite material that these three pieces of patents provide can not reach heat exchanger with the requirement of heating graphite.Comparatively speaking, graphite material according to method preparation of the present invention only need pass through re-baking and greying, technique is simple, for the second time dipping and roasting have for the third time been lacked in its operational path, greatly reduced production cost, and when having improved thermal conductivity, also have higher physical strength and volume density, its excellent combination property.
Claims (10)
1. a heat exchanger is with the preparation method of heating graphite, comprise that fragmentation, screening, batching, kneading, moulding, bakes to burn the article, single-steeping, re-baking and greying obtain finished product, it is characterized in that, described graphite turns to: below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 13-17 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 23-27 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 33-37 ℃/time; Described graphited total time is 120-130h, and described graphited top temperature is 2850-3000 ℃; Preferably, described graphite turns to: below 1000 ℃ the time, the temperature rise rate of graphitizing furnace is 15 ℃/h; In the time of 1000-1500 ℃, the temperature rise rate of graphitizing furnace is 25 ℃/h; In the time of 1500-2100 ℃, the temperature rise rate of graphitizing furnace be 35 ℃/time.
2. preparation method according to claim 1 is characterized in that, in the described graphitizing furnace, the spacing of greying graphite is 100-120mm, and filler is pure graphitized coke, and the granularity of described pure graphitized coke is 10-35mm.
3. preparation method according to claim 1, it is characterized in that, described batching is: the weight ratio of compound and mid-temperature pitch is 78-80:20-22, and described compound is after-smithing petroleum coke and pitch coke, and the weight ratio of described after-smithing petroleum coke and pitch coke is 65-70:30-35; Preferably, the weight ratio of described compound and mid-temperature pitch is 80:20, and the weight ratio of described after-smithing petroleum coke and pitch coke is 70:30.
4. according to preparation method claimed in claim 1, it is characterized in that the particle size range of described after-smithing petroleum coke and content are:
0.7mm＜particle diameter≤0.5mm 10%-25%,
0.5mm＜particle diameter≤0.335mm 25%-30%,
0.335mm＜particle diameter≤0.075mm 20%-25%,
Particle diameter＜0.075mm 30%-40%;
Particle size range and the content of described after-smithing petroleum coke are preferably:
0.7mm＜particle diameter≤0.5mm 15%-20%,
0.5mm＜particle diameter≤0.335mm 27%-29%,
0.335mm＜particle diameter≤0.075mm 20%-23%,
Particle diameter＜0.075mm 33%-37%;
The granularity of described pitch coke is less than 0.075mm.
5. according to preparation method claimed in claim 1, it is characterized in that, described bakes to burn the article is: the temperature of igniting is 220-230 ℃, the top temperature of bakes to burn the article is 1100-1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.6-2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8-1.1 ℃/h, and 500-850 ℃ temperature rise rate is 2.0-2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5-3.5 ℃/h; Filler granularity around the bakes to burn the article product is 2-6mm; Distance between bakes to burn the article product and the wall with flues is not less than 150mm.
6. according to preparation method claimed in claim 1, it is characterized in that described single-steeping is: the graphite behind the bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, floods 5-7h under 1.85-2.0Mpa pressure.
7. according to preparation method claimed in claim 6, it is characterized in that described single-steeping is: under 1.85-1.90Mpa pressure, flood 2-3h first, be forced into again under the 1.90-2.0Mpa and flood 2-3h.
8. according to claim 1 or 6 or 7 described preparation methods, it is characterized in that described soaker is impregnating pitch, in the described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
9. according to preparation method claimed in claim 1, it is characterized in that, described re-baking is: the temperature of igniting is 220-230 ℃, the top temperature of re-baking is 1100-1150 ℃, wherein the temperature rise rate below 400 ℃ is 1.6-2.0 ℃/h, 400-500 ℃ temperature rise rate is 0.8-1.1 ℃/h, and 500-850 ℃ temperature rise rate is 2.0-2.3 ℃/h, and the temperature rise rate more than 850 ℃ is 2.5-3.5 ℃/h; Filler granularity around the re-baking product is 2-6mm; Distance between re-baking product and the wall with flues is not less than 150mm.
10. the heat exchanger of each described preparation method's preparation of claim 1-8 is with heating graphite, it is characterized in that, described heat exchanger with the physicochemical property parameter of heating graphite is: resistivity≤8.0 μ Ω m, folding strength 〉=13Mpa, ultimate compression strength 〉=32Mpa, volume density 〉=1.75g/cm
3, thermal expansivity≤3.2*10
-6/ ℃, thermal conductivity 〉=110W/mk, void content≤20%; Preferably, described resistivity≤7.0 μ Ω m, folding strength 〉=17Mpa, ultimate compression strength 〉=39Mpa, volume density 〉=1.80g/cm
3, thermal expansivity≤3.0*10
-6/ ℃, thermal conductivity 〉=120W/mk, void content≤15%.
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| CN103539109A (en) * | 2013-10-29 | 2014-01-29 | 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 |
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| CN106220178A (en) * | 2016-07-20 | 2016-12-14 | 湖南省长宇新型炭材料有限公司 | A kind of heat exchanger graphite material and preparation method thereof |
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