CN102849729B - 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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- CN102849729B CN102849729B CN201210315816.4A CN201210315816A CN102849729B CN 102849729 B CN102849729 B CN 102849729B CN 201210315816 A CN201210315816 A CN 201210315816A CN 102849729 B CN102849729 B CN 102849729B
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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 heating graphite and preparation method thereof for a kind of heat exchanger.
Background technology
In recent years along with the fast development in heat exchanger market, people significantly improve manufacturing the requirement of interchanger material.For solve strong corrosive media heat transfer problem, improve its heat transfer coefficient, and adapt to heat exchange and energy-conservation needs under high temperature and high pressure condition, the interchanger that people make type material starts to note.General interchanger is all made some with metallic substance and has been started for making the anti-corrosion interchanger of non-metallic material, as graphite heat exchanger.When using for heat exchanger, there is the deficiencies such as corrosion-resistant, the easy fouling of heat-transfer surface, tension and bending strength are low in currently available products, production and use cost have greatly been increased, be unfavorable for the sale of this series products and popularize, developing target market is had to inhibition, 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 meets: 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/ ℃
-1; It is high that graphite material of the present invention has thermal capacity, and thermal conductivity is high, long service life, low cost and other advantages.Its preparation method is: by raw material by screening, batching, kneading, the material that dries in the air, vibratory compaction, again after roasting, dipping, re-baking, greying, 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 is 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 comprises the following 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 meet the demand of heating graphite for heat exchanger.
In view of this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide the preparation method of heating graphite for a kind of heat exchanger, described preparation method, by improving technique, has greatly improved the physicochemical property parameter of the finished product, can meet the demand of heating graphite for heat exchanger.
Another object of the present invention is to provide a kind of heating graphite for heat exchanger that adopts above-mentioned preparation method to prepare.
In order to realize object of the present invention, the following technical scheme of special employing:
The preparation method of heating graphite for a kind of heat exchanger, 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 ℃ 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 ℃.
In the preparation technology of graphite, graphited heating curve directly affects the degree of graphitization of charcoal piece and the physicochemical property of graphite product, it is compound that after-smithing petroleum coke and pitch coke are take in the present invention, 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, contriver is through experiment repeatedly, finally determine below 1000 ℃ time, adopt slower speed to heat up, after this, speed faster with 23-27 ℃/h between 1000-1500 ℃ heats up, between 1500-2100 ℃, further improving speed 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, make the greying conversion of the two tend to consistent as far as possible, greying is effective.In addition, in 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 of preparing under the condition of simplification operational path still has very excellent over-all properties.
Preferably, described graphite turns to: below 1000 ℃ 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 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.
Contriver finds after deliberation, different greying fillers have considerable influence to the physical strength of greying product, heat conductivility and conductivity, as take carbon black and can improve the physical strength of graphite products as filler, but the heat conductivility of graphite products and electroconductibility are had to negative impact.It is filler that the present invention selects to take the graphitized coke of 10-35mm granularity, and after greying, graphite products has higher ultimate compression strength, folding strength and thermal conductivity and lower resistivity.
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, as the large percentage of after-smithing petroleum coke in 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., contriver is through research repeatedly, according to above-mentioned formula, prepare burden, finally obtained the graphite product with 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 400 ℃ of following temperature rise rates are 1.6-2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8-1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0-2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5-3.5 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.
Described single-steeping is: the graphite after bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, and the vacuum tightness in impregnating autoclave is-0.086Mpa that injection soaker floods 5-7h under 1.85-2.0Mpa pressure.
Preferably, described single-steeping is: the graphite after bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, and the vacuum tightness in impregnating autoclave is-0.086Mpa to inject soaker, first under 1.85-1.90Mpa pressure, flood 2-3h, then be forced under 1.90-2.0Mpa and flood 2-3h.
When dipping, first the carbon element product of need dipping are first vacuumized, the object vacuumizing is the gas of discharging in the carbon element product open pores that needs dipping, is beneficial to the infiltration of impregnating pitch.Add after impregnating pitch, under the effect of pressure, impregnating pitch goes than being easier to be penetrated in the hole of the carbon element product that need dipping, thereby guarantees rate of body weight gain.The present invention is in the process of single-steeping, first under certain original pressure, flood, the quinoline containing in soaker in steeping process not fusant can form thin film on the pickled product surface of porous, hinder the infiltration of soaker to 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 in the viscosity, quinoline insolubles content, coking value of pitch.Coking value is higher, after roasting, the volume density of product and physical strength are larger, and coking value increases with softening temperature rising, therefore adopt impregnating pitch that softening temperature is higher as cakingagent, be conducive to improve volume density and the physical strength of graphite material, but impregnating pitch softening temperature is higher, relative viscosity is just larger, is difficult to be penetrated in the hole of pickled product go.Asphalt viscosity was affected by nature both, was just inversely proportional to again with Heating temperature.For improving dipping effect, in the present invention, described soaker is impregnating pitch, in 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 400 ℃ of following temperature rise rates are 1.6-2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8-1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0-2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5-3.5 ℃/h; Re-baking product filler granularity is around 2-6mm; Distance between re-baking product and wall with flues is not less than 150mm.
The object of roasting is to make binder pitch charing, forms coke grid between particles of aggregates, and varigrained aggregate is bonded to an integral body securely.Small-particle formula is when preparing 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 the factor such as heating curve when optimizing and improving roasting of granularity, 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.Three roastings of the present invention adopt identical roasting curve, it is low-temperature ignition, 400 ℃ of following temperature rise rates are 1.6-2.0 ℃/h, lightweight fugitive constituent in 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 temperature-rise period, and light component there is the sufficient time to discharge roasting product; In 400-500 ℃ of roasting product, polycondensation strengthens, coke starts to form, temperature rise rate with 0.8-1.1 ℃/h heats up, the coking rate that is conducive to improve 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 roasting product in the process of polycondensation to crack when shrinking; 850 ℃ of above temperature rise rates are 2.5-3.5 ℃/h, the further densification of weave construction of roasting product.
The heat exchanger of preparing according to foregoing preparation method by 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 heat exchanger by 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 improving preparation technology, heating curve and the impregnation method when optimizing and improving Graphitizing Furnace Rise Temprature Process Curve, roasting particularly, the graphite material of preparation has extraordinary over-all properties, can be used for heating graphite for heat exchanger, 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 adopting is also the equipment that this area is known altogether.
Embodiment 1
Batching: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 80:20.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 1.6 ℃/h, the temperature rise rate of 400-500 ℃ is 1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0 ℃/h, and 850 ℃ of above temperature rise rates are 3.5 ℃/h; Bakes to burn the article product filler granularity is around 6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 340 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa that injection impregnating pitch floods 7h under 1.85Mpa pressure.In 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 400 ℃ of following temperature rise rates are 1.6 ℃/h, the temperature rise rate of 400-500 ℃ is 1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0 ℃/h, and 850 ℃ of above temperature rise rates are 3.5 ℃/h; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 78:22.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8 ℃/h, the temperature rise rate of 500-850 ℃ is 2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 380 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa that injection impregnating pitch floods 5h under 2.0Mpa pressure.In 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 400 ℃ of following temperature rise rates are 2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8 ℃/h, the temperature rise rate of 500-850 ℃ is 2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5 ℃/h; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 78:22.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8 ℃/h, the temperature rise rate of 500-850 ℃ is 2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 380 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa that injection impregnating pitch floods 5h under 2.0Mpa pressure.In 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 400 ℃ of following temperature rise rates are 1.6 ℃/h, the temperature rise rate of 400-500 ℃ is 1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0 ℃/h, and 850 ℃ of above temperature rise rates are 3.5 ℃/h.; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 80:20.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 380 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa, injects impregnating pitch, first under 1.85Mpa pressure, floods 2h, then is forced under 1.90Mpa pressure and floods 3h.In 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 80:20.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 380 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa, injects impregnating pitch, first under 1.90Mpa pressure, floods 3h, then is forced under 2.0Mpa pressure and floods 2h.In 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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: after-smithing petroleum coke is made after broken, screening to 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%, be placed in 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 preparing is put in kneading pot and is dry mixed, after mixing, add mid-temperature pitch to carry out wet mixing, the compound that wherein after-smithing petroleum coke and pitch coke form and with the weight ratio of mid-temperature pitch be 80:20.Thickener after 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 and 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm.Whole temperature-rise period is controlled with temperature alarming instrument, guarantees that the temperature range of temperature alarming instrument is in 5 ℃, roasting product flawless.
After charcoal piece after bakes to burn the article is preheating to 380 ℃, enter impregnating autoclave, the vacuum tightness in impregnating autoclave is-0.086Mpa, injects impregnating pitch, first under 1.85Mpa pressure, floods 3h, then is forced under 1.90Mpa pressure and floods 2h.In 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 400 ℃ of following temperature rise rates are 1.8 ℃/h, the temperature rise rate of 400-500 ℃ is 1.0 ℃/h, the temperature rise rate of 500-850 ℃ is 2.2 ℃/h, and 850 ℃ of above temperature rise rates are 3.0 ℃/h; Roasting product filler granularity is around 2-6mm; Distance between roasting product and wall with flues is not less than 150mm.
Charcoal piece after re-baking is put into greying circuit and carry out greying, below 1000 ℃ 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 the impact of different preparation methods on graphite products performance perameter.
First group of graphite material for preparing according to the method for the embodiment of CN201110115307.2 4, and adopt the general method in this area to measure its physicochemical property parameter;
Second group of graphite material for preparing according to the method for the embodiment of CN201010263217.3 8, and adopt the general method in this area to measure its physicochemical property parameter;
The 3rd group of graphite material for preparing according to the method for the embodiment of CN201010263739.3 7, and adopt 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 obtaining through three roastings greying, operational path is comparatively complicated, production cost is high, and indivedual physical and chemical parameters are lower, as lower in thermal conductivity or physical strength is lower, the over-all properties of the graphite material that these three pieces of patents provide can not reach the requirement of heating graphite for heat exchanger.Comparatively speaking, the graphite material of preparing according to method of the present invention only need pass through re-baking and greying, technique is simple, dipping and roasting for the third time for the second time in its operational path, have been lacked, greatly reduced production cost, and when having improved thermal conductivity, also there is higher physical strength and volume density, its excellent combination property.
Claims (9)
1. the preparation method of heating graphite for a heat exchanger, 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 ℃ 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 ℃;
Described single-steeping is: the graphite after bakes to burn the article enters impregnating autoclave after being preheating to 340-380 ℃, first under 1.85-1.90Mpa pressure, floods 2-3h, then is forced under 1.90-2.0Mpa and floods 2-3h;
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;
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 400 ℃ of following temperature rise rates are 1.6-2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8-1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0-2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5-3.5 ℃/h; Bakes to burn the article product filler granularity is around 2-6mm; Distance between bakes to burn the article product and wall with flues is not less than 150mm;
Described re-baking is: the temperature of igniting is 220-230 ℃, the top temperature of re-baking is 1100-1150 ℃, wherein 400 ℃ of following temperature rise rates are 1.6-2.0 ℃/h, the temperature rise rate of 400-500 ℃ is 0.8-1.1 ℃/h, the temperature rise rate of 500-850 ℃ is 2.0-2.3 ℃/h, and 850 ℃ of above temperature rise rates are 2.5-3.5 ℃/h; Re-baking product filler granularity is around 2-6mm; Distance between re-baking product and wall with flues is not less than 150mm.
2. preparation method according to claim 1, is characterized in that, described graphite turns to: below 1000 ℃ 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.
3. preparation method according to claim 1, is characterized in that, in 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.
4. preparation method according to claim 1, is characterized in that, 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.
5. 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:
The granularity of described pitch coke is less than 0.075mm.
6. according to preparation method claimed in claim 5, it is characterized in that, the particle size range of described after-smithing petroleum coke and content are:
7. preparation method according to claim 1, is characterized in that, the soaker of dipping use is impregnating pitch, in described impregnating pitch: the content ﹤ 4% of quinoline insolubles; Coking value ﹥ 50%.
8. heating graphite for the heat exchanger that prepared by the preparation method described in a claim 1-7 any one, it is characterized in that, described heat exchanger by 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%.
9. according to heating graphite for heat exchanger claimed in claim 8, it is characterized in that 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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| 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 |
| CN105712343B (en) * | 2014-12-03 | 2019-01-08 | 大同新成新材料股份有限公司 | The graphite product for opening wide the method for circular furnace roasting fine-grained structure graphite product and being obtained by this method |
| CN105645386B (en) * | 2014-12-03 | 2018-11-02 | 大同新成新材料股份有限公司 | High purity graphite stove graphite furnace lining and preparation method thereof |
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| CN106220178B (en) * | 2016-07-20 | 2020-01-10 | 湖南长宇科技发展有限公司 | Graphite material for heat exchanger and preparation method thereof |
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| CN108101045A (en) * | 2017-12-18 | 2018-06-01 | 大同新成新材料股份有限公司 | A kind of preparation method of carbon product |
| CN108147404B (en) * | 2017-12-25 | 2020-02-07 | 大同新成新材料股份有限公司 | Graphite product with super-large specification and graphitization method thereof |
| CN109192946B (en) * | 2018-08-28 | 2022-04-19 | 大同新成新材料股份有限公司 | Preparation method of titanium-based lithium ion negative electrode material |
| CN109809386A (en) * | 2019-04-02 | 2019-05-28 | 四川启明星铝业有限责任公司 | The method that ring-form calcining furnace is used for lithium cell cathode material carbonation process |
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