CN101331082A - Original coal and stock oil composition for needle coke and for electricity storing carbon material - Google Patents
Original coal and stock oil composition for needle coke and for electricity storing carbon material Download PDFInfo
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Abstract
A stock oil composition as a stock oil for production of needle coke or for production of an active carbon for electric double layer capacitor electrode, comprising a first heavy oil of 300 DEG C or higher initial boiling point, 12 mass percent or less asphaltene contents, 50 mass percent or more saturated contents and 0.3 mass percent or less sulfur contents as obtained by vacuum distillation of petroleums as residual oil and a second heavy oil of 150 DEG C or higher initial boiling point and 0.5 mass percent or less sulfur contents as obtained by fluid catalytic cracking of hydrocarbon oil.
Description
Invention field
The present invention relates to be used to produce the feedstock composition of accumulate carbon material and needle coke and just burnt.Specifically, the feedstock composition that is applicable to the activated carbon of producing the double-layer capacitor electrode and first Jiao who the present invention relates to provide residual alkali metal wherein to be easy to remove.The invention still further relates to and be applicable to feedstock composition and first Jiao who produces needle coke.
Background of invention
In recent years, carbon material is widely used in the accumulate field.In the accumulate carbon material, the activated carbon with large surface area is the electrode as double-layer capacitor, and less Jiao of surface-area is the negative electrode as lithium-ions battery.Particularly double-layer capacitor receives publicity because of it can be used as standby power supply, accessory power supply etc., for this reason, has extensively launched various researchs at the performance of the activated carbon that is used as the double-layer capacitor electrode.Activated carbon is splendid aspect electrostatic capacitance as the double-layer capacitor of polarizable electrode, thereby along with the development of electronic applications, and the demand as such electrical condenser of various electrical equipment electrodes is increased fast.And, add reducing of conventional storage standby power supply size in recent years, carried out the research that is used as the products with larger capacity of motor accessory power supply to various.
The preparation method of these activated carbon normally for example uses the alkali activation treatment of alkali metal hydroxide as activator with carbonaceous material through gas or chemical activation treatment, by remove basic metal and heavy metal with strong acid example hydrochloric acid, nitric acid and sulfuric acid scrubbing described activated material is neutralized then.
With regard to high performance double-layer capacitor, more and more need to reduce as basic metal residual quantity in the activated carbon of electrode for capacitors.But, described by patent document 1 (the Japanese Patent spy opens 2005-123462), by can making basic metal be removed to finite concentration with acid or water washing repeatedly, but to further remove just difficulty of metal.Therefore, contain double-layer capacitor through alkali activatory carbon material fine aspect the initial capacitance device capacity, but shortcoming is can be in time and deterioration, condenser capacity has very big loss behind the life-time service.
On the other hand, with regard to carrying out washing treatment, expect simply as far as possible, expect that promptly washing times is the least possible, with the reduction expense.Patent document 2 (international publication number WO2004/011371) is addressed can be by carrying out the alkali activation treatment with easy graphited carbonaceous material, washs according to the described activation products of inferior ordered pair of hot water, Soda Ash Light 99.2min., hot hydrochloric acid, ammoniacal liquor, hot hydrochloric acid and hot water then to prepare activated carbon.But this carrying out washing treatment process is tediously long, therefore needs exploitation to have the activated carbon that can be easy to remove the residual alkali metal construction strongly.
Needle coke with aggregate form as Graphite Electrodes used in the EAF Steelmaking Process and normally produce as raw material with petroleum base heavy oil or coal tar.In producing the process of Graphite Electrodes, coke granule and pitch binder applied is mixed with the reservation ratio, limit heating edge kneading and extrude mold pressing and produce the base electrode next life then.Graphitization processing and assembling are carried out in the green electrode calcining, produced the Graphite Electrodes product thus.
The thermal expansivity of Graphite Electrodes (CTF) is preferably lower, because of it is to use under severe condition such as hot conditions.That is it is little thereby reduced the cost of Electric furnace steel making, to have the graphite electrode consumption of low CTF.
Above-mentioned graphitizing process be one with green electrode about 3000 ℃ down heating processes and use direct current furnace (LWG stove) usually.But the graphitizing process that carries out in the LWG stove can quicken temperature and rise, thereby improves the gas formation speed.Might cause taking place abnormal swelling, promptly so-called inflatable.Inflatable can reduce the density of electrode, and electrode is broken.
Now, conduct a research at the method that heats the coefficient of expansion and inflatable in the time control of production needle coke, and proposed the whole bag of tricks.For example patent document 3 (the Japanese Patent spy opens 5-105881) the suitable oligopolymer that discloses the coal-tar pitch that will remove quinoline insolubles substantially and the polymerization degree mixes and carries out pyrogenic method with delayed coking process.Patent document 4 (the Japanese Patent spy opens 5-163491) discloses coal-tar base heavy oil and petroleum base heavy oil is mixed so that nitrogen and sulphur content are respectively 1.0% (quality) or lower and 1.4% (quality) or lower by specific proportions, make raw material, put it into then and generate green coke in the delay coking device, afterwards green coke is calcined and cooling calcining once more under 1200-1600 ℃ down in 700-900 ℃.Patent document 5 (the Japanese Patent spy opens 5-202362) discloses in coal fast pyrolysis method and has produced in the process of coal tar, making the thermo-cracking temperature maintenance in the reactor is 5 seconds or shorter 750 ℃ or the higher and residence time of thermal cracking products in reactor, thus next life production fluid body product or product liquid pitch, the method for then pitch of product liquid or product liquid being carried out carbonization.Patent document 6 (the Japanese Patent spy open 7-3267 disclose by will as the petroleum base heavy oil of raw material separately or the delayed coking of its miscellany with the coal-tar base heavy oil of removing quinoline insolubles substantially handle and also make described petroleum base heavy oil be adjusted to particulate matter subsequently such as ash oontent is the method that 0.05-1% (quality) produces needle coke.
But arbitrary method of above-mentioned patent document 3-6 may not be certain to reduce satisfactorily thermal expansivity or suppresses inflatable, and practical situation are can not reach the level that the used Graphite Electrodes aggregate of EAF Steelmaking Process requires by the coke quality that these methods are produced.
Summary of the invention
The present inventor investigates further and studies intensively the feedstock production process that activated carbon is just expected, found that, when activated carbon be by specific raw material is mixed and coking and will obtain as first Jiao's coal during through the alkali activation treatment, it has the structure that can make washings be easy to pass through, thereby can reduce in the activated carbon basic metal residual quantity and can simplify washing operation.
And, find that the coefficient of expansion of calcining the needle coke of being produced by first Jiao that the feedstock composition coking with above-mentioned specific material combination is generated is enough little and be enough to suppress inflatable.
Term used herein " just burnt " is meant the carbonized product of producing by with heavy oil or residuum coking, is the first material of activated carbon or needle coke.
Promptly, the present invention relates to comprise first heavy oil, its initial boiling point is that 300 ℃ or higher, asphalt content are that 12% (quality) or lower, saturates content are that 50% (quality) or higher and sulphur content are 0.3% (quality) or lower, and described first heavy oil is that the residual oil that vacuum distilling obtains as petroleum based oil is produced; With second heavy oil, its initial boiling point is that 150 ℃ or higher and sulphur content are 0.5% (quality) or lower, is that hydrocarbon ils is produced through fluid catalytic cracking.
The invention still further relates to by with above-mentioned raw materials composition first Jiao that coking is produced under 300-800kPa pressure and 400-600 ℃ of temperature.
The invention still further relates to by the above-mentioned just burnt or above-mentioned just burnt thermal treatment product that thermal treatment generated under barometric point and 550-900 ℃ of temperature is activated the activated carbon of being produced with alkali metal hydroxide.
The invention still further relates to and contain the double-layer capacitor of above-mentioned activated carbon as electrode materials.
The invention still further relates to the needle coke of producing in 800-1600 ℃ of temperature lower calcination by with above-mentioned Jiao just.
The invention effect
Activated carbon of the present invention is by being that first Jiao that specific heavy oil mixture coking is generated carries out alkali and activates and produce with feedstock composition of the present invention.Activated carbon has the structure that can make washings be easy to pass through, and the residual alkali amount of metal is reduced.The electrode that this activated carbon is used for double-layer capacitor can make its cycle characteristics improve.And this activated carbon can make washing operation simplify, thereby has reduced production cost.Therefore, the industrial value of this activated carbon is high.Needle coke of the present invention be by first Jiao that raw material coking of the present invention is generated calcine produce.The thermal expansivity of this needle coke is enough little and be enough to suppress inflatable.
Implement optimal mode of the present invention
Below the present invention will be described in more detail.
Of the present inventionly just burntly be applicable to first Jiao who produces activated carbon or needle coke, comprise the mixture of the heavy oil that the heavy oil with specified property (being called first heavy oil herein) produced by petroleum based oil vacuum distilling and hydrocarbon ils produce through fluid catalytic cracking with specified property with feedstock composition.
Being used for first heavy oil of the present invention and being initial boiling point and be 300 ℃ or higher, asphalt content and be 12% (quality) or lower, saturates content and be 50% (quality) or higher and sulphur content is 0.3% (quality) or lower heavy oil, is that the residual oil that vacuum distilling obtains as petroleum based oil is produced.
These examples as the petroleum based oil of first heavy oil feedstock comprise air distillation residual oil and the mixing oil thereof that crude oil, crude distillation are produced.
Condition to raw material (petroleum based oil) vacuum distilling does not have particular determination, as long as boiling point, asphalt content, saturates content and sulphur content meet above-mentioned requirements.But pressure is preferably 30kPa or lower and temperature is preferably 400 ℃ or higher.
As the heavy oil fraction that vacuum distillation process residual oil is produced, promptly boiling point, asphalt content, saturates content and sulphur content satisfy the component of above-mentioned requirements as first heavy oil of the present invention.
Promptly the boiling point of first heavy oil is necessary for 300 ℃ or higher, preferred 350 ℃ or higher.The initial boiling point of not preferred first heavy oil is lower than 300 ℃, because first Jiao that just burnt output can reduce and obtain has non-crystal structure, makes residual alkali amount of metal increase in the activated carbon of being produced by first burnt alkali activation.The upper limit of initial boiling point be preferably 450 ℃ or lower, more preferably 400 ℃ or lower.
The first heavy oil medium pitch matter content be necessary for 12% (quality) or lower, be preferably 10% (quality) or lower, 9% (quality) or lower more preferably.The not preferred first heavy oil medium pitch matter content is higher than 12% (quality), because coking can take place too early, generation has first Jiao of low-crystallinity coke structure, makes by first burnt alkali and activates the thermal expansivity height that the residual alkali amount of metal increases and just Jiao calcines the needle coke of being produced in the activated carbon of being produced.The lower bound of asphalt content is 0% (quality).
In first heavy oil saturates content be necessary for 50% (quality) or higher, be preferably 55% (quality) or higher, 60% (quality) or higher more preferably.Saturates content is lower than 50% (quality) in not preferred first heavy oil, because the intermediate phase alignment capabilities is very poor, first Jiao of gained has the coke structure of low-crystallinity, and the just burnt thermal expansivity of calcining the needle coke of being produced is raise.The upper limit of saturates content is preferably 85% (quality) or lower, 80% (quality) or lower more preferably.
The first sulfur in heavy oil content be necessary for 0.3% (quality) or lower, be preferably 0.2% (quality) or lower, 0.1% (quality) or lower more preferably.The not preferred first sulfur in heavy oil content is higher than 0.3% (quality), because as if can cause too early coking, generation has first Jiao of poor degree of crystallinity coke structure, makes residual alkali amount of metal in the activated carbon of being produced by first burnt alkali activation increase and be not enough to suppress ballooning in the needle coke that just burnt calcining produced.
The second used heavy oil of the present invention is that initial boiling point is that 150 ℃ or higher and sulphur content are 0.5% (quality) or lower heavy oil, is that hydrocarbon ils is produced through fluid catalytic cracking.
Term " fluid catalytic cracking " is meant high boiling fraction solid acid cracked method.Fluid catalytic cracking unit in these class methods is also referred to as " FCC unit ".
Hydrocarbon ils as second heavy oil feedstock is not had particular determination, get final product so long as hydrocarbon ils satisfies above-mentioned requirements through the initial boiling point of heavy oil that fluid catalytic cracking is produced and sulphur content.But preferably use 15 ℃ of lower densities to be 0.8g/cm
3Hydrocarbon ils.
The example of this class hydrocarbon ils comprises straight run gas oil, vacuum gas oil, desulfurization gas oil, desulfurization vacuum gas oil, air distillation residual oil, vacuum distilling residual oil, shale oil, sandstone rock asphalt oil, Orinoco tar, coal synthetic oil, the product of these oil acquisitions of hydrofining and their mixture.Among the present invention, especially preferably adopt vacuum gas oil and desulfurization vacuum gas oil.
Condition to fluid catalytic cracking does not have particular determination, gets final product so long as initial boiling point and sulphur content satisfy the heavy oil of above-mentioned requirements.For example, preferable reaction temperature is 480-550 ℃, and stagnation pressure is 1-3kg/cm
2G (98-294kPa gauge pressure), catalyst/oil ratio are that 1-20wt/wt and duration of contact are 1-10 second.
The example of fluid catalytic cracking catalyst system therefor comprises silica catalyzer, zeolite catalyst and the catalyzer of loaded metal such as platinum on it.These catalyzer markets can get.
Like this initial boiling point of second heavy oil of Sheng Chaning be necessary for 150 ℃ or higher, preferred 200 ℃ or higher, more preferably 220 ℃ or higher.Not preferred initial boiling point is lower than 150 ℃ second heavy oil, because first Jiao that first Jiao's output can reduce and obtain has non-crystal structure, make the thermal expansivity rising that the residual alkali amount of metal increases and calcine by first Jiao the needle coke of being produced in the activated carbon of being produced by first burnt alkali activation.The upper limit of initial boiling point be preferably 350 ℃ or lower, more preferably 300 ℃ or lower.
The second sulfur in heavy oil content be necessary for 0.5% (quality) or lower, be preferably 0.4% (quality) or lower, 0.3% (quality) or lower more preferably.The not preferred first sulfur in heavy oil content is higher than 0.5% (quality), because as if can cause too early coking, generation has first Jiao of poor degree of crystallinity coke structure, makes residual alkali amount of metal in the activated carbon of being produced by first burnt alkali activation increase and be not enough to suppress ballooning in the needle coke that just burnt calcining produced.
Nitrogen content to second heavy oil does not have particular determination, but is preferably 0.2% (quality) or lower, more preferably 0.15% (quality) or lower, 0.1% (quality) or lower more preferably.Second heavy oil that nitrogen content is higher than 0.2% (quality) will make the needle coke that obtains be not enough to suppress ballooning.
Feedstock composition of the present invention is produced by above-mentioned first and second heavy oil are mixed.
With regard to the ratio of mixture that described raw material is first and second heavy oil when being used to produce the used activated carbon of the electrode of double-layer capacitor, by first heavy oil preferably account for 10-80% (quality), more preferably 20-70%, more preferably the amount of 30-60% is mixed them.With regard to the ratio of mixture that described raw material is first and second heavy oil when being used to produce the coke of needle coke, by first heavy oil preferably account for 1-50% (quality), more preferably 5-50%, more preferably the amount of 15-50% is mixed them.
In next step, feedstock composition of the present invention is carried out coking handle.
The example of feedstock composition coking method comprises delayed coking process, viscosity breaking method, flexicoking method, Eureka method and H-Oil method, wherein particularly preferably is delayed coking process.
In delayed coking process, described feedstock composition is put into delay coking stove and heating under stress.Pressure in the delay coking stove is preferably 300-800kPa.The temperature of delay coking stove is preferably 400-600 ℃, more preferably 450-550 ℃.The residence time is 24-72 hour, is preferably 36-60 hour.
The result that coking is handled is the carbonized product (green coke) that generates as just burnt.
Among the present invention, contain that the feedstock composition of first and second heavy oil is preferably a kind of to provide during heating 10 μ m or littler pattern structure ratio to be less than 5% or lower, preferred 2% or lower first Jiao's composition down at 500 ℃ when this raw material.Here the ratio of 10 μ m or littler pattern structure is less among first Jiao means that the liquid crystal growth conditions that is called intermediate phase is fine.Intermediate phase is with generation polycondensation of raw material heat treatment process and the resulting intermediate product of thermolysis, and is to generate because of the wide area aromatic ring along same planar development.
Just the pattern structure among Jiao is that 147 pages description is measured in " the base carbon chemical industry journey " of being shown by Yuzo Sanada and SugiroOtani that Ohmsha company publishes.
Up to now, except that the polymerization of aromatic component and polycondensation, also can take place crosslinked when thinking the raw material coking of high saturates content, particularly high aliphatic thing content always, thereby generation three-dimensional crystal growth, cause intermediate phase can not fully grow and differ from the structure of degree of crystallinity, the coefficient of expansion of gained needle coke can increase like this, and the basic metal residual quantity increases in the gained activated carbon.Consider this point, though the saturates content of first heavy oil be 50% or higher but still can produce 10 μ m or littler pattern structure ratio be less than 5% or lower coke be unexpected.
First Jiao that coking is produced can change into activated carbon by the alkali activation.Burnt originally when activate by alkali, preferably inert atmosphere and normal pressure and 550-900 ℃, just implement the alkali activation treatment after with first burnt thermal treatment preferred 600-850 ℃ time.
Among the present invention, the activated carbon of Sheng Chaning is as the electrode materials of double-layer capacitor like this.
Just burnt or its thermal treatment product can activate by under nitrogen atmosphere or inert atmosphere and normal pressure and 500-1200 ℃ itself and metal hydroxides being heated in activation furnace.The example of metal hydroxides comprises alkali metal hydroxide such as potassium hydroxide, sodium hydroxide and lithium hydroxide and alkaline earth metal hydroxides such as magnesium hydroxide and hydrated barta.These metal hydroxidess can be used singly or in combination.In these metal hydroxidess, preferably use potassium hydroxide, because because it can effectively form micropore.
Amount just burnt or its thermal treatment product and metal hydroxides is recently fixed with quality, can be 1/0.5-1/10, preferred 1/1-1/5.
Mass ratio just burnt or its thermal treatment product and metal hydroxides be 1/0.5 or more the young pathbreaker might produce and have the sufficient amount micropore and enough activated carbon of high surface area.Mass ratio just burnt or its thermal treatment product and metal hydroxides be 1/10 or more senior general might effectively activate and not reduce bulk density.
In priming reaction, just burnt or its thermal treatment product and metal hydroxides can with coexistence such as water.
Just in Jiao or its thermal treatment product reactivation process, activation temperature can be 500-1200 ℃, preferred 600-1000 ℃, more preferably 600-800 ℃.Activation temperature might effectively be produced the activated carbon with sufficient amount micropore in this temperature range.Soak time is appropriately selected according to correlated response condition such as temperature, for example can be 3-6 hour.
The used rare gas element of reactivation process comprises indifferent gas and nitrogen.Preferred supplied for inert gas is so that the oxygen concentration in the activation phenomenon maintains 100ppm (volume) or still less.
So that separate solid and liquid, method can be activation products are immersed and to mix with washings, if necessity can stir and heat, shifts out washings then by activation products are washed activation products with the method for washings washing.Washings is preferably water or aqueous acid.For example, available any suitable array mode such as water, aqueous acid and again water wash activation products.The example of aqueous acid comprises haloid acid such as spirit of salt, hydroiodic acid HI and Hydrogen bromide and mineral acid such as sulfuric acid and carbonic acid.The concentration of aqueous acid can be 0.01-3N.If need, available these washings repetitive scrubbings repeatedly.
In the washing operation, after the last washing of above-mentioned washings, solid is separated with washings, suitably heating and dry air shift out moisture then, obtain activated carbon thus.
The characteristics of carrying out the activated carbon that the alkali activation produced by first Jiao that feedstock composition coking of the present invention is generated are that the residual alkali amount of metal is less than traditional active carbon when adopting the same manner to wash.It is believed that reason that the alkali metal hydroxide residual quantity reduces is that Jiao just of the present invention has activator alkali metal hydroxide and washings and is easy to crystalline structure by first Jiao.
In addition, electrolyte ion might pass through through it when the characteristics of activated carbon of the present invention were charging and discharge when being used as the electrode of double-layer capacitor, thereby be improved aspect the electrostatic capacitance retention rate, described electrostatic capacitance retention rate adopts cycle characteristics to test and estimates.
Double-layer capacitor of the present invention comprises electrode, and described electrode comprises that the thermal treatment product by first Jiao that feedstock composition of the present invention is made or first Jiao activates the activated carbon of being produced.
Electrode to double-layer capacitor of the present invention does not have particular determination, as long as it comprises above-mentioned activated carbon.Electrode can comprise binding agent, conductive agent etc. and integrate one with collector electrode.
Binding agent can make any conventional binders.Specific examples comprises polyolefine such as polyethylene and polypropylene, fluorinated polymer such as tetrafluoroethylene, poly(vinylidene fluoride) and crosslinked fluoroolefin/vinyl ether co-polymer, Mierocrystalline cellulose such as carboxymethyl cellulose, vinyl polymer such as polyvinylpyridine and polyvinyl alcohol, and polyacrylic acid.The amount of binding agent is 0.1-30% (quality) in the electrode.
The specific examples of conductive agent comprises powdered material such as carbon black, acetylene black and powdered graphite.The content of conductive agent is preferably 1-50% (quality), 2-30 quality % more preferably
Adopt the example of the method for these material produce electrodes to comprise above-mentioned activated carbon, binding agent and conductive agent joined and make slurry in the solvent that can dissolve binding agent and be applied to the method on the sheet collector electrode and above-mentioned activated carbon, binding agent and conductive agent mediated without these solvents but under room temperature or intensification condition and the method for mold pressing.
Collector electrode can be that any well known materials is made and have traditionally shaped collector electrode that the specific examples of collector electrode comprises metal such as aluminium, titanium, tantalum and nickel and alloy such as stainless steel.
Double-layer capacitor of the present invention can be made battery, one is disposed opposite to each other by barrier film as negative pole as anodal another and impregnated in the electrolytic solution in the wherein above-mentioned pair of electrodes, and barrier film can be polypropylene fibre or glass fibre non-woven or cellulose paper.
Electrolytic solution can be water system or non-aqueous electrolyte, but non-aqueous electrolyte preferably.The example of non-aqueous electrolyte comprises by ionogen being dissolved in the electrolytic solution of making in the organic solvent.The specific examples of solvent comprises, propylene carbonate, ethylene carbonate, carbonic acid fourth diester, gamma-butyrolactone, tetramethylene sulfone, tetramethylene sulfone derivative such as 3-methyl sulfolane, glycol dimethyl ether be as 1,2-glycol dimethyl ether, acetonitrile, trimethylene cyanide, valeronitrile, dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), methyl-formiate, methylcarbonate, diethyl carbonate, ethylmethyl carbonate.These solvents can be used singly or in combination.The electrolytical example of electrolytic solution comprises inorganic ion salt such as an alkali metal salt and alkaline earth salt, quaternary ammonium salt, and the ring-type quaternary ammonium salt is with quaternary alkylphosphonium salt etc.Specific examples comprises (C
2H
5)
4NBF
4, (C
2H
5)
3(CH
3) NBF
4, (C
2H
5)
4PBF
4(C
2H
5)
3(CH
3) PBF
4Electrolytical concentration can be 0.1-5mol/L and is preferably 0.5-5mol/L in the electrolytic solution.
Double-layer capacitor of the present invention can adopt sheet or the circular electrode of Any shape such as a pair of thick 50-500 μ m and be placed on barrier film between them and be contained in a button shaped, the stacked shape that pair of electrodes is arranged with multilayered structure by the rolled-up curved of barrier film, many counter electrode and the barrier film between them in the metal box.
Double-layer capacitor of the present invention presents improved cycle characteristics and splendid weather resistance and electric capacity retention rate because of using above-mentioned electrode.
The feedstock composition that will contain above-mentioned first and second heavy oil carries out first Jiao that coking produces can be converted into needle coke by it is calcined in rotary kiln or shaft furnace.Calcining temperature is preferably 800-1600 ℃, more preferably 1000-1500 ℃.Calcination time is 1-10 hour, is preferably 2-6 hour.
The sulphur content of preferred needle coke of the present invention is that 0.5% (quality) or lower and nitrogen content are 0.1% (quality) or lower.
The thermal expansivity of needle coke of the present invention is enough little and can effectively suppress inflatable.
Traditionally, using the inflatable inhibitor is the method for known inhibition inflatable.But the inflatable inhibitor may become impurity, and counter electrode quality (particularly thermal expansivity and density) has disadvantageous effect.And the advantage of needle coke of the present invention is not use this class inflatable inhibitor just can fully suppress inflatable and thermal expansivity is enough low.
Needle coke of the present invention is suitable for use as the Graphite Electrodes aggregate of EAF Steelmaking Process.The method of producing the Graphite Electrodes product with needle coke comprises mediates the needle coke of the present invention and the suitable first material of the mixture of the binder pitch of add-on, heat simultaneously and extrude, make fresh electrode thus, come graphitizing method by calcining and typing then.
Term used herein " sulphur content " be meant respectively oil by JIS K 2541 and coke by value that JISM8813 measured.Term used herein " nitrogen content " is meant the value that oil is measured by JIS M8813 by JIS K 2609 and coke respectively.Term used herein " saturates content " and " asphalt content " are meant the value that adopts tlc determination.
Industrial application
Just burnt feedstock composition of the present invention is applicable to the activated carbon of producing the double-layer capacitor electrode, also is applicable to the production needle coke.
Embodiment
Describe the present invention in more detail with reference to the following example, but be not to limit the present invention.
Embodiment 1
With air distillation residual oil (density 0.92g/cm
3Sulphur content: be that 350 ℃ and pressure are to carry out vacuum distilling under the condition of 1.3kKp in the furnace outlet temperature 0.35% (quality)), producing initial boiling point thus and be 410 ℃, asphalt content is that 9% (quality), saturates content are that 61% (quality), sulphur content are that 0.1% (quality) and nitrogen content are the vacuum distilling residual oil (hereinafter being called vacuum distilling residual oil A) of 0.3% (quality).
A puts into test tube with vacuum distilling residual oil, and coking was carried out in normal pressure and 500 ℃ of following heating in 3 hours.To observe in the coke embedding commercial resins of producing like this and by polarizing microscope.Find to exist the 10 μ m or the littler pattern structure of 15% (quality).
In addition, with desulfurization vacuum gas oil (sulphur content: 500ppm (quality), 15 ℃ of density: 0.88g/cm
3) carry out fluid catalytic cracking, produce fluid catalytic cracking residual oil (hereinafter being called " fluid catalytic cracking residual oil A ").The initial boiling point of the fluid catalytic cracking residual oil A of Sheng Chaning is that 210 ℃, sulphur content are that 0.1% (quality), nitrogen content are that 0.1% (quality), asphalt content are that 0% (quality) and saturates content are 34% (quality) like this.
A puts into test tube with fluid catalytic cracking residual oil, and coking was carried out in normal pressure and 500 ℃ of following heating in 3 hours.The coke of producing embeds in the commercial resins and by polarizing microscope and observes like this.Found that and do not have 10 μ m or little pattern structure.
(2) preparation is just burnt
Next, vacuum distilling residual oil A and fluid catalytic cracking residual oil A are mixed with 3: 7 mass ratio, make feedstock composition A.With the feedstock composition A that makes like this coking 40 hours under 400kPa pressure and 500 ℃ of temperature, generate coke (first burnt A) thus.To observe in the first burnt A embedding commercial resins that generate like this and by polarizing microscope.Found that the 10 μ m or the littler pattern structure that there are 3.5% (quality).
(3) Jiao's activation just
The mixture of 1 part (quality) first burnt A and 2.5 parts of (quality) potassium hydroxide (KOH) is put into a nickel reactant device, in nitrogen atmosphere, under 750 ℃ of temperature, heated 1 hour.
After the activation, the reaction mixture in the container is cooled to 300 ℃ temperature, sends into carbonic acid gas and replace nitrogen and make the potassium metal inactivation.Afterwards, 20kg water is joined in the 2kg reaction product, stirred 1 hour pressure filtration then under the room temperature.Repeat this step twice.Then, add the 0.3N hydrochloric acid of 20kg in the products therefrom and stirred pressure filtration 3 hours.After adding 20kg water again, mixture was stirred 1 hour and pressure filtration.This step also repeats twice.The solid that obtains like this is dry under 130 ℃, produce the activated carbon that is used for double-layer capacitor thus.The specific surface area of activated carbon, potassium residual quantity and true specific gravity are listed in the table below 1.
(4) preparation double-layer capacitor
Activated carbon (0.8g), ketjen black (0.1g) and tetrafluoroethylene (0.1g) are mixed in mortar.Mixture being clipped in two triacetate films of thickness of 0.1mm, is the rolling between rod of rolling of 0.7mm at a pair of 160mm broad gap, and applied pressure is 23.0MPa.This roll extrusion operation repeats 20 times.By the roll extrusion sheet material stamping-out circular piece that to become two diameters be 16mm and as carbon dioxide process carbon electrode.With carbon dioxide process carbon electrode vacuum drier inner drying 2 hours.
Two electrodes are immersed the electrolytic solution ((C of 1mol
2H
5)
3(CH
3) NBF
4Be dissolved in 1 liter of propylene carbonate).Accompany one the 50 thick Mierocrystalline cellulose barrier film of μ m between electrode, electrode and barrier film are put into and be packaged in SUS 316 button cells of a diameter 20mm.Immediately, respectively prepare a collector electrode, be clipped in respectively between battery and the carbon electrode then, make coat side carbon electrode by the aluminium foil surface that carbon coating is coated 20 μ m thickness as collector electrode.
The electrostatic capacitance of the double-layer capacitor of making like this and cycle characteristics (repeated charge 1000 times after electrostatic capacitance retention rate) are listed in table 1.
Embodiment 2
Vacuum distilling residual oil A and fluid catalytic cracking residual oil A are mixed with 6: 4 mass ratio, make feedstock composition B.With the feedstock composition B that makes like this coking 40 hours under 400kPa pressure and 500 ℃ of temperature, generate coke (first burnt B) thus.Press the step operation of embodiment 1, difference is that the mixture of 1 part (quality) first burnt B and 2.5 parts of (quality) potassium hydroxide (KOH) is put into a nickel reactant device, in nitrogen atmosphere, under 750 ℃ of temperature, activate 1 hour, make the used activated carbon of double-layer capacitor.The specific surface area of activated carbon, potassium residual quantity and true specific gravity are listed in the table below 1.Adopt the step identical, make double-layer capacitor with this activated carbon with embodiment 1.The electrostatic capacitance of the double-layer capacitor of making like this and cycle characteristics (repeated charge 1000 times after electrostatic capacitance retention rate) are listed in table 1.
Comparing embodiment 1
Only with fluid catalytic cracking residual oil A coking 40 hours under 400kPa pressure and 500 ℃ of temperature, adopt the step identical to carry out the alkali activation treatment afterwards with embodiment 1.Prepare double-layer capacitor with the activated carbon of making like this.The electrostatic capacitance of the specific surface area of activated carbon, potassium residual quantity and true specific gravity and the double-layer capacitor made like this and cycle characteristics (repeated charge 1000 times after electrostatic capacitance retention rate) are listed in table 1.
Comparing embodiment 2
Only with vacuum distilling residual oil A coking 40 hours under 400kPa pressure and 500 ℃ of temperature, adopt the step identical to carry out the alkali activation treatment afterwards with embodiment 1.Prepare double-layer capacitor with the activated carbon of making like this.The electrostatic capacitance of the specific surface area of activated carbon, potassium residual quantity and true specific gravity and the double-layer capacitor made like this and cycle characteristics (repeated charge 1000 times after electrostatic capacitance retention rate) are listed in table 1.
From the listed result of table 1 as can be seen, can reduce potassium residual quantity in the activated carbon by vacuum distilling residual oil is mixed the feedstock composition of the present invention that is generated with fluid catalytic cracking residual oil.The result is when described activated carbon is used to produce double-layer capacitor, can improve the electrostatic capacitance retention rate.
| Embodiment 1 | Embodiment 2 | Comparing embodiment 1 | Comparing embodiment 2 | |
| Feedstock composition | Feedstock composition A (3: 7 mixtures of vacuum distilling residual oil A and fluid catalytic cracking residual oil A) | Feedstock composition B (6: 4 mixtures of vacuum distilling residual oil A and fluid catalytic cracking residual oil A) | Fluid catalytic cracking residual oil A | Vacuum distilling residual oil A |
| Activated carbon | ||||
| Specific surface area m 2/g | 1600 | 1800 | 1600 | 2200 |
| Potassium residual quantity ppm | 62 | 51 | 150 | 120 |
| Double-layer capacitor | ||||
| Electrostatic capacitance F/CC | 25 | 27 | 26 | 25 |
| Electrostatic capacitance retention rate % | 91 | 92 | 87 | 89 |
Embodiment 3
Vacuum distilling residual oil A and fluid catalytic cracking residual oil A are mixed with 1: 1 mass ratio, make feedstock composition C.Feedstock composition C put into test tube and under 400kPa pressure and 500 ℃ of temperature heating carried out coking in 40 hours.To observe in the first burnt C embedding commercial resins that generate like this and by polarizing microscope.Found that the 10 μ m or the littler pattern structure that there are 3.5% (quality).
First burnt C was calcined 5 hours down at 1000 ℃, make calcined coke (needle coke) thus.Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Section burnt mix with the coal-based binder pitch of 30% (quality) and be shaped to the cylindrical particle thing through forcing machine.The cylindrical particle thing was calcined 1 hour down in 1000 ℃ in retort furnace, measured the thermal expansivity of column particulate matter afterwards.Then, particulate matter is heated to 2800 ℃ and measure turgidity the heat-processed as the inflatable rate from room temperature.The results are shown in table 2.
Embodiment 4
Vacuum distilling residual oil A and fluid catalytic cracking residual oil A are mixed with 1: 5 mass ratio, make feedstock composition D.Feedstock composition D put into test tube and under 400kPa pressure and 500 ℃ of temperature heating carried out coking in 40 hours.To observe in the first burnt D embedding commercial resins that generate like this and by polarizing microscope.Found that the 10 μ m or the littler pattern structure that there are 2.5% (quality).
First burnt D was calcined 5 hours down at 1000 ℃, make calcined coke thus.Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Adopt the step identical but make the cylindrical particle thing with section burning of preparing above and measure thermal expansivity and inflatable rate, the results are shown in table 2 with embodiment 3.
Embodiment 5
Vacuum distilling residual oil A and fluid catalytic cracking residual oil A are mixed with 1: 3 mass ratio, make feedstock composition E.Feedstock composition E put into test tube and under 400kPa pressure and 500 ℃ of temperature heating carried out coking in 40 hours.To observe in the first burnt E embedding commercial resins that generate like this and by polarizing microscope.Found that the 10 μ m or the littler pattern structure that there are 3.0% (quality).
First burnt E was calcined 5 hours down at 1000 ℃, make calcined coke thus.Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Adopt the step identical but make the cylindrical particle thing with section burning of preparing above and measure thermal expansivity and inflatable rate, the results are shown in table 2 with embodiment 3.
Comparing embodiment 3
Vacuum distilling residual oil A put into test tube and under 400kPa pressure and 500 ℃ of temperature heating carried out coking in 40 hours.First Jiao who generates was like this calcined 5 hours down at 1000 ℃, make calcined coke thus.Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Adopt the step identical but make the cylindrical particle thing with section burning of preparing above and measure thermal expansivity and inflatable rate, the results are shown in table 2 with embodiment 3.
Comparing embodiment 4
Fluid catalytic cracking residual oil A put into test tube and under 400kPa pressure and 500 ℃ of temperature heating carried out coking in 40 hours.First Jiao who generates was like this calcined 5 hours down at 1000 ℃, make calcined coke thus.Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Adopt the step identical but make the cylindrical particle thing with section burning of preparing above and measure thermal expansivity and inflatable rate, the results are shown in table 2 with embodiment 3.
Comparing embodiment 5
With sulphur content is that 0.2% (quality), nitrogen content are that 0.3% (quality) and saturates content are that the sweet crude oil of 40% (quality) carries out vacuum distilling, and generating initial boiling point and be 410 ℃, asphalt content is that 12% (quality), saturates content are that 40% (quality), sulphur content are that 0.2% (quality) and nitrogen content are the vacuum distilling residual oil (hereinafter being called vacuum distilling residual oil B) of 0.3% (quality).B puts into test tube with vacuum distilling residual oil, and coking was carried out in heating in 40 hours under 400kPa pressure and the 500 ℃ of temperature.First burnt the embedding in the commercial resins and by polarizing microscope of producing like this observed.Find to exist the 10 μ m or the little pattern structure of 18% (quality).
Afterwards, will just burntly calcine 5 hours down, make calcined coke thus at 1000 ℃.
Empyreumatic sulphur of making like this of section and nitrogen content and bulk specific gravity are listed in table 2.
Adopt the step identical but make the cylindrical particle thing with section burning of preparing above and measure thermal expansivity and inflatable rate, the results are shown in table 2 with embodiment 3.
Table 2
| Sulphur content (quality %) | Nitrogen content (quality %) | Bulk specific gravity | Thermal expansivity * 10 -6/℃ | Inflatable rate (%) | |
| Embodiment 3 | 0.2 | 0.4 | 0.81 | 1.4 | 0.4 |
| Embodiment 4 | 0.2 | 0.2 | 0.82 | 1.3 | 0.2 |
| Embodiment 5 | 0.2 | 0.3 | 0.84 | 1.3 | 0.2 |
| Comparing embodiment 3 | 0.4 | 0.7 | 0.78 | 2.0 | 1.1 |
| Comparing embodiment 4 | 0.1 | 0.1 | 0.84 | 1.8 | 0.1 |
| Comparing embodiment 5 | 1.5 | 0.7 | 0.78 | 2.0 | 1.1 |
Claims (9)
1. just burnt feedstock composition, comprising the initial boiling point as residual oil of being produced by petroleum based oil vacuum distilling and be 300 ℃ or higher, asphalt content and be 12% (quality) or lower, saturates content and be 50% (quality) or higher and sulphur content is 0.3% (quality) or the first lower heavy oil; With the initial boiling point of producing by the fluid catalytic cracking of hydrocarbon ils experience be that 150 ℃ or higher and sulphur content are 0.5% (quality) or the second lower heavy oil.
2. by the feedstock composition of claim 1, wherein said petroleum based oil is selected from air distillation residual oil and the mixing oil thereof that crude oil, crude distillation are produced.
3. by the feedstock composition of claim 1, wherein said hydrocarbon ils is selected from the product of straight run gas oil, vacuum gas oil, desulfurization gas oil, desulfurization vacuum gas oil, air distillation residual oil, vacuum distilling residual oil, shale oil, sandstone rock asphalt oil, Orinoco tar, coal synthetic oil, the acquisition of hydrofining any one or more these oil.
4. by the feedstock composition of claim 1, wherein when when heating down for 500 ℃ it the ratio of 10 μ m or littler pattern structure can be provided is 5% or lower first Jiao.
5. by will under 300-800kPa pressure and 400-600 ℃ of temperature, carrying out first Jiao that coking is produced by the arbitrary feedstock composition of claim 1-4.
By will by first Jiao of claim 5 or under normal pressure and 550-900 ℃ of temperature this just burnt its thermal treatment product that is generated of heating carry out the activated carbon that the alkali activation treatment is produced with alkali metal hydroxide.
7. comprise by the activated carbon of claim 6 double-layer capacitor as electrode.
8. by inciting somebody to action the just burnt needle coke of producing in 800-1600 ℃ temperature lower calcination.
9. by the needle coke of claim 8, wherein sulphur and nitrogen content are respectively 0.5% (quality) or lower and 0.1% (quality) or lower.
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| JP2005375926A JP4809675B2 (en) | 2005-12-27 | 2005-12-27 | Petroleum coke and method for producing the same |
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| JP2006293963 | 2006-10-30 | ||
| JP293963/2006 | 2006-10-30 | ||
| PCT/JP2006/326368 WO2007074938A1 (en) | 2005-12-27 | 2006-12-27 | Original coal and stock oil composition for needle coke and for electricity storing carbon material |
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| CN105883750A (en) * | 2016-04-14 | 2016-08-24 | 神华集团有限责任公司 | Mesoporous carbon and preparation method thereof |
| CN106068574A (en) * | 2014-03-04 | 2016-11-02 | 捷客斯能源株式会社 | Artificial graphite for negative electrode of lithium ion secondary battery material and manufacture method thereof |
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| EP2336267B1 (en) | 2008-09-09 | 2017-04-05 | JX Nippon Oil & Energy Corporation | Process for producing needle coke for graphite electrode and stock oil composition for use in the process |
| JP6339105B2 (en) | 2013-12-24 | 2018-06-06 | Ｊｘｔｇエネルギー株式会社 | Petroleum needle coke and method for producing the same |
| JP6651305B2 (en) * | 2015-07-09 | 2020-02-19 | Ｊｘｔｇエネルギー株式会社 | Manufacturing method of petroleum needle coke for graphite electrode |
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| JPH05105881A (en) * | 1991-10-16 | 1993-04-27 | Nippon Steel Chem Co Ltd | Manufacture of needle coke |
| JP3093015B2 (en) * | 1991-12-12 | 2000-10-03 | 新日鐵化学株式会社 | Needle coke manufacturing method |
| JPH05202362A (en) * | 1992-01-24 | 1993-08-10 | Nippon Steel Chem Co Ltd | Production of acicular coke |
| JPH073267A (en) * | 1993-06-14 | 1995-01-06 | Nippon Steel Chem Co Ltd | Production of needle coke |
| CN1169911C (en) * | 2001-11-14 | 2004-10-06 | 中国科学院山西煤炭化学研究所 | Method for preparing needle coke |
| JP4238830B2 (en) * | 2002-07-30 | 2009-03-18 | クラレケミカル株式会社 | Activated carbon, manufacturing method thereof, polarizable electrode, and electric double layer capacitor |
| JP2004247433A (en) * | 2003-02-12 | 2004-09-02 | Nippon Oil Corp | Raw-material coal composition of carbon material for electrodes of electric double-layer capacitor |
| JP4054746B2 (en) * | 2003-10-17 | 2008-03-05 | 新日本石油株式会社 | Electric double layer capacitor, activated carbon for the electrode, and manufacturing method thereof |
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| CN106068574A (en) * | 2014-03-04 | 2016-11-02 | 捷客斯能源株式会社 | Artificial graphite for negative electrode of lithium ion secondary battery material and manufacture method thereof |
| CN106068574B (en) * | 2014-03-04 | 2019-03-12 | 捷客斯能源株式会社 | Artificial graphite for negative electrode of lithium ion secondary battery material and its manufacturing method |
| CN105883750A (en) * | 2016-04-14 | 2016-08-24 | 神华集团有限责任公司 | Mesoporous carbon and preparation method thereof |
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