CN1159421A - Porous carbon material containing minute pores, and process for preparing the same - Google Patents

Porous carbon material containing minute pores, and process for preparing the same Download PDF

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CN1159421A
CN1159421A CN 96121741 CN96121741A CN1159421A CN 1159421 A CN1159421 A CN 1159421A CN 96121741 CN96121741 CN 96121741 CN 96121741 A CN96121741 A CN 96121741A CN 1159421 A CN1159421 A CN 1159421A
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stabilization
softening point
carbonization
temperature
molded article
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CN1069603C (en
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槌谷正俊
中岛亮一
铃木清贵
重松等
西谷胜利
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Maruzen Petrochemical Co Ltd
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Maruzen Petrochemical Co Ltd
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Priority claimed from JP8018327A external-priority patent/JPH09188565A/en
Priority claimed from JP8090032A external-priority patent/JPH09255320A/en
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Abstract

The invention discloses a bitumen-based porous carbon material with high specific surface area and small pores, the prepare method and the intermediate material: stabilized bitumen-based material. The manufacture method of bitumen-based porous carbon material is that: firstly heavy oil or bitumen with specific characteristics such as containing H/C atom ratio and BTX insoluble content is made to micro materials, secondly organic solvent is used to extract the micro materials so as to remove the light components in the micro materials, thereby obtaining a micro material that softening point is 180 DEG or higher measured by the method of temperature grads, the displayed weight loss is 5wt percent or lower after heated at 300 DEG, and no components are insoluble to the BTX solvent basically.

Description

Contain porous carbon materials of aperture and preparation method thereof
The present invention relates to contain the porous carbon materials of aperture, this material can be used as the molecular absorption agent, the adsorptivity separating agent, catalyzer, the functionalization gac, with be used for electrode as material at double layer capacitor, relate to the molded article that makes from porous carbon materials and relate to stable bituminous material, this bituminous material is the intermediate raw material of porous carbon materials.The invention still further relates to the method for making these materials.
The carbon material that contains aperture that with the gac is representative can be used as the adsorptivity separating agent.
In recent years, having diameter is that the carbon material of the following micropore of 10 dusts or 10 dusts is used to separate and reclaim nitrogen and carbonic acid gas.Separation and recovery oxygen and nitrogen (this has caused that people note greatly) just are to use an example of the technological method of this porous carbon materials from air.Specifically, the whole bag of tricks for this purpose and the exploitation of material for example, are the exploitations that is called the method that pressure-swing absorbs (PSA) (wherein gas is adsorbed and passes through the pressure reduction desorption), be called the exploitation of the porous carbon materials of molecular-sieve carbon (MSC) or carbonaceous molecular sieve (CMS), or the like.
And, it is reported, the capacity of lithium-ion secondary cell (its market enlarge rapidly) in recent years is the influence (" Minute Pore Structure ofCarbon and Secondary Battery Performance (small structure of carbon and the performance of secondary cell) " pp190-191 for example, Summary of the Lecture for the 1994 Meeting of theCarbon Society of Japan (1994 Japanese carbon association annual meeting report collection of thesis)) that is subjected to as the small structure of the carbon of negative potential.The porous carbon materials that contains aperture also can be used as the electrode in the double layer capacitor.By this way, the utilization of porous carbon materials in other field except common adsorption separation technology field further enlarges.
In the past, mainly be that activation method is used to make the porous carbon materials that contains aperture.These activation methods comprise a kind of in the atmosphere that has oxidizing gas such as steam, carbonic acid gas or oxygen the method for heat treated carbon formed material such as cocoanut charcoal, charcoal or coke; Allow char-forming material mix with compound such as zinc chloride, phosphoric acid, potassium hydroxide or salt of wormwood and this mixture heating up is caused the combined thing corroding method of char-forming material perhaps a kind of comprising.Yet the porous carbon materials that is made by these methods has wide pore size distribution.Thereby the very difficult porous carbon materials that obtains to have uniform pore size.
For this reason, once the someone has recommended several method to reduce pore size distribution and has made minimum hole.Be included in and in the example of these methods of using with the method for making carbon material by carbon laydown be: with oil as coal tar or creosote, or with producing the organic compound of carbon such as the gac that resin impregnating has wide pore size distribution through heating, heat resulting material has the new carbon of small-bore and narrow pore size distribution with production method (USP4 then, 458,022, the open No. of Japanese Patent is clear and 61 (1986)-191510, USP4,742,040); Be included in to heat in the atmosphere that contains gaseous organic compound and have the process of active carbon of non-homogeneous pore size distribution, this compound deposit carbon and cause that carbon deposits in the hole after heating, thus aperture (USP3,801 reduced, 513, the open No. of Japanese Patent clear and 60 (1985)-171212); And similar approach.
Yet these methods need raw material carbonizing treatment at high temperature, activation treatment at high temperature and be used to produce with deposit carbon so that the pyroprocessing of gac aperture homogenizing.At high temperature the needs of this three steps processing make operation become complicated and cause the cost raising.Homogeneity at resulting carbon material mesopore also is not enough.
Also there is the people once to propose freshly prepd carbon and do not need complicated activation treatment or sedimentary other method.Example is with the carbonization and change into carbon in addition in statu quo or after stable resin under the situation that does not need to melt of resin material such as polyvinylidene chloride, resol or melamine resin, so that assorted element that contains in resin such as chlorine, oxygen, nitrogen are as HCl, CO, CO 2, H 2O, NO, N 2, HCN or analogue discharge, thereby (the open No. of Japanese Patent is clear and 50 (1975)-161485 to produce the method for aperture, the open No. of Japanese Patent is clear and 52 (1977)-77017, the open No. of Japanese Patent is clear and 57 (1982)-118009, Japanese Patent disclose No. clear and 61 (1986)-6108).Yet this method needs special thermosetting resin as raw material, and this raw material can produce a large amount of objectionable impuritiess in carbonization process.It is too expensive to be not only thermosetting resin, and the objectionable impurities that is discharged must be handled by the method for high cost.
Someone had once proposed to use the method for the spinning asphalt (spinning pitch) of more cheap high softening-point as raw material.In this method, spinning asphalt is transformed into powdery or fibrous material by efflorescence or spinning, stablized by introducing oxygen, produce pore (USP4 with being carbonized afterwards by discharging the oxygen of being carried secretly, 734,394, the open No. of Japanese Patent puts down 6 (1994)-142503, the open No. flat 6 (1994)-144818 of Japanese Patent).This method also needs complicated processing, as being the thermal treatment that high softening point bitumen adopted of manufacturing as starting raw material.The unstable of this manufacture method is another shortcoming.
These a large amount of carbon materials are to use with the form of molded article such as particulate material, sheet stock or pelletizing.For this reason, under the situation of granular, pulverous or fibrous carbon material fine,, also need develop the method that is used for making porous formed goods except exploitation is used for controlling the pore structure of carbon material and the method for pore size distribution.
The example of these class methods comprises following each method: allow useless metachloroethylene copolymer carry out the desalination acid treatment, this material is pulverized, with allow it and agglutinant such as coal-tar pitch, petroleum pitch or caking coal and granulating agent such as abisel, waste molasses or sulfite pulp be mixed together, with mixture pelleting, a kind of method of carbonization (the open No. of above-mentioned Japanese Patent clear and 50 (1975)-161485) in inert atmosphere subsequently; Allow vinylidene chloride polymer carry out the desalination acid treatment, this material is pulverized, material crushed with softening temperature be granulation after the derivatived cellulose of 50-150 ℃ pitch and cellulose crystallite coagulum, water soluble or carbohydrate are mixed together, subsequently in inert atmosphere a kind of method of carbonization (the open No. of Japanese Patent is clear and 52 (1977)-75691, above-mentioned Japanese Patent disclose No. clear and 52 (1977)-77017); Allow coconut powdered carbon and binding agent such as coal tar or coal-tar pitch mix, with the mixture granulation and carry out destructive distillation, use creosote treatment, and a kind of method of carbonization in inert atmosphere (above-mentioned USP4,742,040); Allow the powder of resol or melamine resin mix, with mixture pelleting and a kind of method of carbonization (Japanese Patent open No. flat 4 (1992)-280810) in inert atmosphere then with binding agent such as coal tar, pitch or creosote; Pitch spinned fiber with high softening-point, make fibrous pitch stable, its granulation is produced agglomerated thing, add polyvinyl alcohol, starch, resol or bituminous solution or dispersion liquid as binding agent with produce three-dimensional fiber mesh network (wherein agglomerated thing solidifies) and then in inert atmosphere with a kind of method (the open No. of Japanese Patent puts down 6 (1994)-157018) of network carbonization; With allow the high softening point bitumen spinning produce fibrous material, make this fibrous material stable, allow this material mix with pitch (softening temperature is 80-150 ℃), resol or furane resin as binding agent, with mixture be shaped as sheet material and then in inert atmosphere with molded article carbonization (Japanese Patent open No. flat 7 (1995)-81915).In these methods, yet the organic substance that is used as binding agent or coalescing agent not necessarily forms hole behind carbonization process.Hole forms and can not cause the medium and small porosity of whole molded article completely after the carbonization, this is pointed as prior art: use too many binding agent can " cause the infringement of the molecular sieve performance of porosity reduction and the finished product " (the open No. of Japanese Patent puts down 6 (1994)-157018, the open No. flat 7 (1995)-81915 of Japanese Patent).
Owing to these reasons, once proposed to provide the several method of aperture again for binding agent.These methods comprise, for example, with the high softening point bitumen spinning, make it stable, binding agent with pitch (softening temperature 80-150 ℃), resol or furane resin and so on is shaped as spherical aggregate with stable product, make the stable once more and a kind of method of carbonization (the open No. flat 6 (1994)-142503 of above-mentioned Japanese Patent) in inert atmosphere then of spherical aggregate; With high softening point bitumen is ground into powder, make powder stable, with the binding agent of pitch (softening temperature 80-150 ℃), resol, furane resin or Resins, epoxy and so on stable powder granulation, make the stable once more and a kind of method of carbonization (the open No. flat 6 (1994)-144818 of above-mentioned Japanese Patent) in inert atmosphere then of particulate matter.The carbon goods that obtained by these methods partly and at filler partly have tiny hole at binding agent or coalescing agent, yet the character difference of the character of carbon and the carbon in the filler part is bigger in binding agent or coalescing agent part.The molded article that forms from the porous carbon materials shaping of being produced by these methods has small structure heterogeneous inevitably.
As mentioned above, make the efficient and economic method of porous carbon materials and still be in developmental stage from the molded article that this material makes with even hole.Molded article with even hole that has only several porous carbon materials and make from it or the method for making them are known at present.
When porous carbon materials being used for many above-mentioned application, important task is to break through technical improvement for the high efficiency method that preparation has the method for the method of porous carbon materials of high specific surface area and control small structure and this porous carbon materials of preparation.
In general, do not considering once had the porous carbon materials of aperture from the raw material manufacturing of carbonization already under the inhomogeneity situation of pore dimension, this carbonized stock is such as being cocoanut charcoal, charcoal or the coke of producing by the former dry distillation of coal, or by the coke of the treatment production of heavy oil.These raw materials or in the oxidizing atmosphere that contains such as steam, carbonic acid gas or oxygen, activated, perhaps activated by following method: allow carbonized stock mix with compound such as zinc chloride, phosphoric acid, potassium hydroxide or salt of wormwood and then heated mixt cause the corrosion of the combined thing of carbonized stock.
It is also known that the type of employed carbon raw material and characteristic influence the character of the porous carbon materials that is obtained widely, as specific surface area and porosity.Also have, once proposed the material standed for of a large amount of carbon raw materials and the activation method except that aforesaid method.Some examples of this class activation method comprise following each method: with the thermal treatment product activatory method of the polyvinyl alcohol and the vitriol oil (the open No. of Japanese Patent clear and 53 (1978)-37594); Aldehyde and acidity or basic catalyst are joined in the distillation residue of primary tar acid and make mixture generation polyaddition reaction, allow resulting resin mix and then with a kind of method of mixture carbonization (the open No. of Japanese Patent clear and 62 (1987)-52114) with pitch; Will be by middle carbon (mesocarbon) the microballon activatory method that separated from solvent reclaimed of optical anisotropy bead, wherein this bead is (the open No. flat 2 (1990)-213357 of Japanese Patent) by the treatment production of heavy oil; By adding the method (the open No. flat 1 (1989)-308818 of Japanese Patent) that alkali such as sodium hydroxide or potassium hydroxide come thermal treatment xylogen or lignin derivative; With hot fusile resol powder in addition carbonization and activatory method (the open No. flat 2 (1990)-43716 of Japanese Patent); And vinyl monomer is joined in the particle of sclerosis novolac resin or fusible type resol, allow mixture carry out polyreaction and then with a kind of method (the open No. flat 3 (1991)-187910 of Japanese Patent) of resulting polymkeric substance carbonization.
Yet these methods have many shortcomings, as the lower velocity of priming reaction, and the processing efficiency of difference, limited by specific surface area or porosity that activation is obtained, the high price of carbon raw material itself, or the like.
Once proposed a kind of the activator (as aqueous potassium hydroxide) that adds specified quantitative and carbon raw material afterwards heat-treating methods come increasing specific surface area (USP4,082,694, USP5,064,805) widely.Then, this method need product must be with a large amount of water washings times over the aqueous potassium hydroxide of the amount of carbon raw material with after thermal treatment.Because this respect, resulting porous carbon materials is expensive inevitably.Also have because the carbon raw material must with the aqueous potassium hydroxide thorough mixing, to guarantee uniform chemical activation effect, resulting porous carbon materials is limited to powder type.When using binding agent with this powder forming or granulation, the specific surface area of resulting product or porosity will be because of different (for example the declines on the condition of priming reaction speed and generation hole, the 32nd Japanese carbon association proceeding in summer, pp39-44).
The present invention's general introduction
Therefore, main purpose of the present invention provides a kind of porousness asphaltic base (pitch-based) carbon material that is rich in aperture with high-specific surface area;
Second purpose provides a kind of porousness pitch base carbon material that is rich in aperture that high-specific surface area is arranged with narrow pore size distribution;
The 3rd purpose provides a kind of porousness pitch base carbon molded article that is rich in aperture with high-specific surface area;
The 4th purpose provides a kind of porousness pitch base carbon molded article that is rich in aperture with high-specific surface area with narrow pore size distribution;
The 5th purpose provides a kind of porousness pitch base carbon preparation methods that is rich in aperture with high-specific surface area;
The 6th purpose provides a kind of porousness pitch base carbon preparation methods that is rich in aperture that high-specific surface area is arranged with narrow pore size distribution;
The 7th purpose provides a kind of preparation method with porousness pitch base carbon molded article that is rich in aperture of high-specific surface area;
The 8th purpose provides a kind of preparation method with porousness pitch base carbon molded article that is rich in aperture of high-specific surface area with narrow pore size distribution; And
The 9th purpose provides a kind of asphaltic base stabilization material, and it is to be used for suitably obtaining the intermediate product of above-mentioned purpose.
All above purposes can realize by using cheap starting raw material on technical scale easily, efficiently, economically and in a suitable manner, and need not to use difficulty and step trouble, as the step of making high softening point bitumen from the raw material heavy oil or the pitch of low softening point by the polyreaction of heat at high temperature or catalytic way, or the like.
Other purpose of the present invention for personnel of the prior art from following be described in detail, embodiment and the accompanying drawing that provides will become fully aware of.
We find, high softening point bitumen, it produce from the heavy oil that special properties is arranged particle, powder or fiber shape little shape (micro-shaped) material and remove light constituent with organic solvent extraction from the material of this little shape and make, can produce char-forming material, if high softening point bitumen is stablized and carbonization in inert atmosphere then by oxidation in oxygen-containing atmosphere with extremely even hole.
Because the high softening point bitumen that obtains at aforesaid method has excellent plasticity and good sintering character, the material of the little shape by can easily obtaining to contain aforementioned stableization as binding agent with this high softening point bitumen is as the molded article of filler.Also have, if this molded article is stabilized and carbonization in inert atmosphere then, also can binding agent partly produce with filler in those similar holes.Thereby find, can obtain the porous carbon molded article formed by even carbon material by this method with uniform small pores.
We also find, the high softening point bitumen that in aforesaid method, produces, promptly from the heavy oil that special properties is arranged produce particle, powder or fiber shape little shape material and remove light constituent and the pitch that makes with organic solvent extraction from the material of this little shape, when stabilized during with carbonization obvious with by the high softening point bitumen of common heat treating method or similar approach manufacturing on performance and use different.As mainly to the result of the research of these unique properties of high softening point bitumen, we find, if this bituminous stabilization product carbonization in oxidizing gas such as carbonic acid gas or steam, the carbonized product that can produce uniform aperture with high speed of reaction and can obtain to have very big specific surface area.
And, porous carbon materials, the molded article of porous carbon materials, asphaltic base stabilization material (it is the intermediate materials of porous carbon materials) also finds it is novel and characteristic material.Finished the present invention based on these discoveries.
Therefore, the present invention at first relates to the manufacture method of the porous carbon materials that is rich in aperture with high-specific surface area, and this method comprises:
(starting raw material)
Use starting raw material, it is a H/C atomic ratio heavy oil in the 0.8-1.2 scope and that be substantially devoid of the component that is insoluble to the BTX solvent, or use the low softening point asphalt that obtains from heavy oil by from heavy oil, removing light constituent, this low softening point asphalt to have the softening temperature (measuring) below 150 ℃ or 150 ℃ and be substantially devoid of the component that is insoluble to the BTX solvent by temperature gradient method;
(the first step)
Form the material of the little shape that is of a size of 100 μ m or particle, powder or fiber shape below the 100 μ m from starting raw material;
(second step)
By allowing the material of little shape contact and from the material of little shape, extract light constituent with organic solvent, this solvent can cause that the material of little shape of 10wt% keeps as insoluble component at least, thus obtain softening temperature be (measure) more than 180 ℃ or 180 ℃ by temperature gradient method, be the high softening point bitumen material of 5wt% or a kind of little shape below the 5wt% and that be substantially devoid of the component that is insoluble to the BTX solvent through being heated to 300 ℃ of shown weight loss that go out;
(the 3rd step)
High softening point bitumen by the little shape of heating in oxygen-containing atmosphere makes it stable, thereby obtains the material of stabilization; With
With the carbonization in statu quo of resulting stabilization material, or will process by mixing, is shaped and make resulting molded article stabilization and the asphaltic base stabilization molded article carbonization that makes as the stabilization material of filler and binder pitch (it be according to the method preparation the same) with the high softening point bitumen material of little shape of in second step, mentioning.
Second aspect present invention relates to and is rich in aperture and has a 300m 2The porous asphalt base carbon material of/g or higher high-specific surface area (being measured by the BET method of using nitrogen absorption), porous carbon materials are by following acquisition: the bituminous material that forms little shape of particle, powder or fiber shape from the heavy oil of H/C atomic ratio in the 0.8-1.2 scope; Use for the bituminous material of organic solvent extraction this little shape of extraction usefulness remove light constituent with obtain softening temperature be 180 ℃ or higher (by temperature gradient method mensuration), through be heated to 300 ℃ of shown weight loss that go out as 5wt% or below the 5wt%, be substantially devoid of component and the high softening point bitumen material a kind of little shape of H/C atomic ratio in the 0.8-1.2 scope that is insoluble to the BTX solvent; Make the high softening point bitumen stabilization; And with the carbonization of asphaltic base stabilization material.
Third aspect present invention relates to the asphaltic base stabilization material, and this material is by being prepared as follows: the bituminous material that forms little shape of particle, powder or fiber shape from the heavy oil of H/C atomic ratio in the 0.8-1.2 scope; Use for the bituminous material of organic solvent extraction this little shape of extraction usefulness remove light constituent with obtain softening temperature be 180 ℃ or higher (by temperature gradient method mensuration), through be heated to 300 ℃ of shown weight loss that go out as 5wt% or below the 5wt%, be substantially devoid of the component that is insoluble to the BTX solvent with a kind of high softening point bitumen material of H/C atomic ratio in the 0.8-1.2 scope; Make this high softening point bitumen stabilization.
The present invention includes various embodiments, the following describes typical embodiment.
A. in the method for above-mentioned first invention, carbonization in 500-1, is carried out under the temperature between 100 ℃ and resulting porous carbon materials has 300m in inert atmosphere 2/ g or higher specific surface area and its aperture are that central aperture is 10 dusts or the following micropore of 10 dusts.
B. in the method for above-mentioned first invention, carbonization in 400-1, is carried out under the temperature between 000 ℃ and resulting porous carbon materials has 400m in oxidizing gas atmosphere 2It is 40 dusts or below 40 dusts that/g or higher specific surface area and aperture have central aperture.
C. in the method for above-mentioned first invention, itself is carbonized stabilization material.
D. in the method for above-mentioned first invention, to mix by stabilization material and binder pitch (it be according to the method preparation the same), form the in addition carbonization of molded article that forms molded article and make the stable and asphaltic base stabilization that makes of this asphaltic base molded article with the high softening point bitumen material of in second step, mentioning.
E. in embodiment D, the method for preparing asphaltic base stabilization molded article is:
(the 4th step)
Allow as the aforementioned stable formed material of filler and binder pitch (it be according to the method preparation the same) with the high softening point bitumen material of in second step, mentioning, according to making that the amount of high softening point bitumen is that a kind of like this ratio of the 20-70wt% of amount of the mixture is mixed, mixture is pulverized on arbitrariness ground, thereby obtains the raw material for shaping usefulness.
(the 5th step)
To be shaped is shaped with raw material, obtains molded article, is 5mm or below the 5mm from the center to the shortest distance of outside surface wherein; With
(the 6th step)
The heating molded article makes filler part and binding agent partially stabilized simultaneously in oxygen-containing atmosphere.
F. in as above second described carbon material of invention; carbon material can be the material of (a) little shape; as particle, powder or fiber; or (b) molded article; and can to have (a) central aperture be 10 dusts or below 10 dusts, or (b) specific surface area is that 400m/g or higher and central aperture are 40 dusts or below 40 dusts.
The summary of accompanying drawing
Fig. 1 is the absorption-desorption isothermal curve from the nitrogen of porous carbonized material under liquid nitrogen temperature that stable pitches are produced under 355 ℃ of embodiment 1;
Fig. 2 has provided at embodiment 1, obtains among comparative example 1 and the comparative example 2, based on the relation between the productive rate of the carbonized product of high softening point bitumen and the specific surface area measured by the BET method;
Fig. 3 is the absorption-desorption isothermal curve from the nitrogen of forming carbon goods under liquid nitrogen temperature that stable molded articles are produced under 355 ℃ of embodiment 7;
Fig. 4 is the absorption-desorption isothermal curve of the nitrogen of shaping porous carbon article under liquid nitrogen temperature of embodiment 8;
Fig. 5 is the adsorption isothermal curve of the nitrogen of porous carbon materials under liquid nitrogen temperature of embodiment 16;
Fig. 6 is the adsorption isothermal curve of the nitrogen of porous carbon materials under liquid nitrogen temperature of embodiment 24;
Fig. 7 is the scanning electron photomicrograph of the porous carbon materials of embodiment 30, and the segmental length shown in the photo below is corresponding to 10 μ m;
Fig. 8 is the adsorption isothermal curve of the nitrogen of porous carbon materials under liquid nitrogen temperature of embodiment 40;
Fig. 9 is the schematic figures that is used for the device of embodiment 46;
Figure 10 is the scanning electron photomicrograph of the microparticle of the high softening point bitumen that obtains by the jet flow stream of using flow velocity 25l/min in embodiment 45; With
Figure 11 passes through to use the scanning electron photomicrograph of the jet space of 130mm apart from the microparticle of the high softening point bitumen that obtains in embodiment 46.
Detailed description of the present invention
In specification of the present invention, term " BTX solvent " or " BTX " refer to arsol, such as benzene, and toluene, dimethylbenzene, ethylo benzene or their mixture. In addition, in specification of the present invention, term " aperture " is to use with general meaning, and term " micropore " is used for representing that diameter is 20 dusts or the following hole of 20 dusts. In addition, term " shaping " is used for covering a wide scope, and is compressing such as granulation, extrusion molding, granulation and similar operations. And term " stabilisation " and " stablizing " are the synonyms as " having given insoluble " and " giving insoluble ".
Initiation material
As initiation material of the present invention, need to use hydrogen/carbon (H/C) atomic ratio to be heavy oil or the pitch of 0.8-1.2. Be lower than 0.8 raw material when the H/C atomic ratio, namely be rich in aromatic component and the raw material that few aliphatic lateral chain is arranged, when being used as initiation material, stablize raw material with the long time in the 3rd step that need to will describe below and/or the 6th step, be material or the molded article of little shape, because the oxidation rate of material is too low. For the same reason, be difficult to stablize raw material by oxidation, i.e. the material of little shape or molded article, for a full due in the middle of whole material, i.e. not only material surperficial but also its inside. In order to stablize fully this material, the oxygen of q.s need to be introduced in the material. For excessive stabilizing material, in the sort of state of the high stable state that namely will describe below, preferably material is oxidizing in the material oxygen concentration to reach best level is saturated a kind of degree. The material of the little shape that makes when the raw material that is lower than 0.8 from the H/C atomic ratio or molded article wish will be exceedingly or when fully being stablized, causing by oxidation that asphalt material is a large amount of on the surface of the material of little shape or molded article consumes or loss, therefore, the use of this class material is inefficient and uneconomic. On the contrary, if there is not fully stable material, namely the inadequate material of oxygen content is used to the present invention, the inside of material will melting or fusing in carburising step (namely the 7th step), and is difficult to acquisition and has the carbon products that high-specific surface area namely is rich in aperture.
With above opposite, if the H/C atomic ratio of pitch is higher than 1.2, namely lack aromatics and the too much aliphatic series that contains, be used as initiation material, the light component extraction step that will describe below is that the rate of recovery is too low in the second step of the present invention. And, the step of the stabilizing material that will describe below, i.e. in the 3rd step of the present invention or the 6th step, the productive rate of needed stabilization material will descend, because the weight decrease speed that is caused by the oxidation Decomposition of material surpasses the introducing speed of oxygen.
In the present invention, as initiation material, need to use heavy oil or the pitch that is substantially devoid of the BTX insoluble component. That is to say that importantly the BTX insolubles content of initiation material is lower than 1wt% (method by the mensuration insoluble component of routine is measured, those as stipulating) in Japanese Industrial Standards (JIS). Because if initiation material contains the BTX insoluble matter, insoluble component can be disturbed the production of material of little shape of the shapes such as micron particles, powder, fiber. In addition, the BTX insoluble component be formed by heat polymerization and similar reaction and have the component of HMW, the compound of highly condensed aromatic ring is namely arranged. Have this compounds of highly condensed aromatic ring not to be suitable for the present invention because they be difficult to oxidized and thereby not only disturb the formation of aperture, and reduce the productive rate of needed product. This is because in the reaction of stablize asphalt material, and oxidation reaction begins with the oxidation of the inside of molecule then very difficult from the marginal portion of molecule. Therefore, if the number of the aromatic ring that contains in highly condensed molecule is higher, oxygen content in molecular weight (average meaning is said) step-down.
In addition, when preparing molded article by method of the present invention, be used as can be used to the binding agent of pitch binder applied base stabilization material by the processing acquisition high softening point bitumen of the following first step that will describe and second step. If initiation material contains a large amount of BTX insoluble component, the high softening point bitumen that obtains from it also can contain a large amount of BTX insoluble component naturally. Be rich in the binding agent of BTX insoluble component, namely high softening point bitumen can not mix or adhere to this material well with the asphaltic base stabilization material. So the heavy oil or the pitch that contain a large amount of BTX insoluble component are inappropriate as initiation material in the present invention.
As the raw material heavy oil that can be used among the present invention, permitted eurypalynous raw material and can use and be illustrated below. Raw material as the oil source, can enumerate the heavy oil that can be obtained by the naphtha cracking (so-called naphtha cracking tar or be called simply naphtha tar), can be by the heavy oil (so-called pyrolytic tar) of gas oil cracking acquisition, the heavy oil (so-called decantation oil or FCC slurry oil) that can be obtained by the fluid catalytic cracking (FCC) of petroleum fractions and similarly oily. In the middle of these oil, naphtha tar especially is fit to, because it contains hetero atom such as sulphur, nitrogen and oxygen hardly. This is because the raw material of naphtha cracking tar is almost by the naphtha of pure hydrocarbon composition. During the tail gas of discharging in processing described carburising step below, it is desirable that the naphtha cracking tar contains the heteroatomic fact hardly.
Heavy oil such as the coal tar itself in coal source are not suitable for the present invention, because the heavy oil in coal source generally has too low H/C atomic ratio, i.e. and high armaticity and usually contain a large amount of BTX insoluble component. Yet even the heavy oil in coal source can be used in the present invention, if its through processing and remove the BTX insoluble component and/or through over hydrogenation or hydrocrack in order to satisfy above-mentioned requirements. As mentioned above, although the heavy oil in coal source can be used in the present invention, but when comparing with the use of the heavy oil in oil source such as naphtha cracking tar, the use of the heavy oil in coal source is inappropriate, because the fringe cost that it also needs preliminary treatment or various preliminary treatment to bring.
As raw material of the present invention, above-mentioned heavy oil itself can use or be no more than 150 ℃ low softening point asphalt by the softening point that temperature gradient method records and also can use.
Term used herein " softening point that is recorded by temperature gradient method " can be determined by following: the long and narrow aluminium sheet heating of thermograde will alongst be arranged, sprinkle sample powder along aluminium sheet, brush away lightly sample, the temperature of that measure then that sample begins to adhere to, thus record softening point. Employed device is Asia Rikaki KK, the product of AMK-B2CEFH-3. The softening point that is recorded by temperature gradient method is approximately lower 15-20 ℃ and than approximately low 25-50 ℃ of the softening point that is recorded by the Mettler method of stipulating among the ASTM than the softening point that is recorded by JIS Ring and Ball (R﹠B) method. Certainly, above-mentioned correlation only can be used to estimate R﹠B softening point or Mettler softening point, and the difference between the softening point of usefulness and R﹠B softening point or the Mettler softening point will change according to type, source and the character of pitch in the present invention.
Work as emulsification method, when film emulsification method or injection method were used as preparing the method (the following first step of the present invention that will describe) of material of little shape, above-mentioned heavy oil itself can use or use after the processing of adjusting viscosity. When low softening point asphalt was selected as initiation material, it was that the solution form (by it being dissolved in the solution that obtains in the suitable solvent) with predetermined viscosity is used. In emulsification method and film emulsification method, preferably raw material under emulsifying temperature, have be not higher than 1,000 the pool viscosity and in injection method, preferably raw material under injection temperation, have be not higher than 20 the pool viscosity. Do not contain the BTX insoluble component because be used for the present invention's raw material, as being used for the organic solvent of raw materials solution, much less the BTX solvent is preferred. Yet other solvent also can use, as long as they can dissolve the above raw material of 90wt%. The example of this type of organic solvent is carbon tetrachloride, chloroform, trichloro-ethylene, the tar gas and oil or the carbonyl oil that obtain from coal tar, and gasoline or the gas oil produced by the naphtha cracking.
The first step
The first step of the present invention is to make material (being particle, powder or the fiber that size the is not more than 100 μ m) step of little shape from the initiation material of above defined.
The reason that arrowhead is not more than 100 μ m is to accelerate evenly to separate in extraction step (being the second step of narrating later) with shortening and remove the needed time of light component. For example, if the raw material that will extract is oversize, be in grade, although can extract fast on the surface of material, the inside of extraction material needs long time. Therefore, if the size of the raw material that will extract is too big and when extraction time was inadequate, extraction can not be carried out equably. Another reason of size that limits the material of little shape is in order to stablize equably stripped material from the material surface to inside in stabilizing step (the 3rd step of the present invention that namely the following describes). If material has big size, although the surface of material can successfully be stabilized at short notice, material internal can not be stabilized at short notice, because the diffusion velocity of oxygen in material can be so not high. If the inside of material does not have sufficiently stabilisation, namely even partly remain on non-steady state, adding afterwards pined for usually can making the material melting or being melted in together. If there is large-sized material attempting from the surface to inside in addition complete stability, the loss that the productive rate of stabilisation product will cause because of near the oxidation of carrying out fast the material surface reduces.
The whole bag of tricks, such as pulverizing, spinning, emulsification or injection, can be as the method for the material of making little shape.
(a) it is desirable to cooling or with pulverize when large quantity of air mixes will mutually be melted in together because of the heat that produces in the crushing process because the softening point of initiation material of the present invention is lower than the various materials of 150 ℃ (being recorded by temperature gradient method) and little shape. As mix the device of pulverizing with large quantity of air, known in the prior art is jet mill.
(b) when the softening point that is recorded by temperature gradient method enough is higher than room temperature, for example be higher than 45 ℃, also can be made by spinning process the material of little shape. Because being used for initiation material of the present invention is substantially devoid of and is insoluble to BTX solvent (benzene, toluene, dimethylbenzene, ethylo benzene or their mixture) component, if be heated to sufficiently high temperature with reduced viscosity to the viscosity of hundreds of in several thousand pool scopes, this material can carry out melt spinning easily. Extrude molten material and the making method of long fibres of the fine fibre that stretches from spinning nozzle, make the centrifugal spinning method of fine fibre from the pitch of being discharged from nozzle by centrifugal force, by the melt air blowing method of the power generation fine fibre of the high-speed gas rapid flow below nozzle, or eddy current method can both be used as spinning process. Temperature than high about 50-70 ℃ of the softening point of the raw material that is recorded by temperature gradient method is preferably used as spinning temperature. Specifically, to be used for the softening point that is recorded by temperature gradient method of the present invention be that 45-150 ℃ low softening point asphalt is preferred to 95-220 ℃ spinning temperature. Because this temperature range enough is lower than the temperature that decomposition or sex change take place common organic material in inert atmosphere, spinning operation can carry out in stable mode, not such as using common high softening point bitumen to make the problem of the decomposition, sex change or the coking that run in the spinning process of asphalt base carbon fiber as raw material. When the softening point of the raw material that is recorded by temperature gradient method hanged down, if cool off fully from the pitch fibers of nozzle ejection, fiber can be melted in together mutually. In this case, by will from the organic solvent that the direct feeding of pitch fibers of nozzle ejection is used, can avoid the fusion between the fiber second step.
(c) in addition, when raw material is softening point when being lower than 45 ℃ raw material or raw material when being liquid at normal temperatures, breaking method or spinning process can not be as the methods of the material of making little shape, thereby, in this case, the material of little shape is by following emulsification method preparation. We have proposed emulsification method in Chinese patent application 95120535.8 (application on December 6 nineteen ninety-five). The method is as follows:
Making fine grain method with high softening point bitumen comprises: the first step, in the presence of surfactant and water, stir raw material heavy oil by stirring means, it is the emulsion of the following tiny spheric granules of 100 μ m or 100 μ m that this stirring means can provide shearing force to produce to have the particle size that is dispersed in water, wherein raw material heavy oil is under agitation to have 1, the liquid of the viscosity that 000 pool or 1,000 pool are following; Second step, allow the emulsion that in the first step, obtains and extraction contact with organic solvent (this solvent can dissolved water with can stay at least the raw material heavy oil of 10wt% is insoluble part), from the tiny spheric granules of emulsion Raw heavy oil, extract and remove light component and dilution organic solvent (using organic solvent if exist to dilute), thereby the fine particle of raw material heavy oil is transformed into the pitch fine particle of the softening point that raising is arranged; With the 3rd step, by the solid-liquid separation method from the emulsion that second step, obtains with extract the pitch fine particle that separates and reclaim the softening point of raising with the liquid mixture of organic solvent.
(d) except the above-mentioned emulsion method of " stirring provides shearing force ", can also adopt the film emulsification method of nearest exploitation. This method uses glass with micron-sized even hole or pottery as emulsifying film medium (emulsification membrane media). The water that contains surfactant circulates as decentralized medium or stirs in a side of this emulsifying film medium, and the material that will disperse, for example heavy oil, pitch or be dissolved in organic solvent or by the solution of the pitch of organic solvent diluting, be forced out by means of the pressure reduction between the emulsifying film medium both sides. Because the even hole of the flow of material Over emulsfication film medium that will disperse when being forced out, this material is dispersed in the water, as size and the proportional particle form of pore-size. Can obtain to have by this way the emulsion particle of narrow size distribution.
Be used for making the method (c) of material of little shape and a feature (d) and be raw material heavy oil or pitch are transformed into emulsion in the water. Emulsification heavy oil or pitch belong to the spherical droplets form because of its surface tension.
(f) in addition, the asphalt material for little shape of the present invention can make by the injection method that the following describes. Can find out that from following narration the first step of the present invention and second step can be carried out by injection method immediately simultaneously.
In the past, injection method was not successfully produced the particle that can be used for little shape of the present invention. That is, the pitch method of injecting with hot gas is difficult to quenching particle in the situation that does not take place to reunite. Usually obtain the bulky grain of reuniting. Oarse-grained existence is disadvantageous for the present invention. Once had one in quench process, to add improving one's methods of inorganic powder, yet shortcoming is that product can not be used for the present invention, because the existence of inorganic powder is disadvantageous.
We find that the material that can be used for little shape of the present invention can make by specific injection method. In the method, by preliminary treatment raw material heavy oil or the pitch that viscosity is adjusted to suitable level is sprayed by means of suitable injection apparatus, obtain to be of a size of 100 μ m or the following oil particles of 100 μ m. Then, so the oil particles of preparation contacts to remove light component and the diluent (if being used for pretreated words) that is contained in the oil particles with extraction immediately with organic solvent. Therefore, be in contact with one another a kind of pitch particle with little shape of high softening-point that can not form aggregate even can produce. The shape of particle without limits and can use any shape, for example sheet is bar-shaped, spherical or even aggregate, if its size is 100 μ m or below the 100 μ m. Use organic solvent as extraction, can use the extraction organic solvent of in the narration of relevant second step, explaining in detail. Perhaps under gas phase, perhaps even under liquid phase, namely in extraction with in the organic solvent, carry out spraying. Oil particles can be undertaken by any suitable method with contacting of organic solvent with extraction, such as (i) oil particles is splashed into extraction with in the organic solvent, (ii) allow from the oil particles of nozzle ejection with contact gas phase from the extraction of other nozzle ejection materials flow with organic solvent, or (iii) use the nozzle the organic solvent to spray raw material heavy oil from immersing extraction.
By using operation sequence (iii) can have many shapes by the material of little shape of used operating condition acquisition, such as sheet, bar-shaped, graininess etc. and the normally spherical or oval particle of material by little shape of using operation sequence (i) or (ii) obtaining. Thereby, when needs are produced spherical or oval particle, preferably use operation sequence (i) or (ii).
To the not specific restriction of type of the injection apparatus that is used for spraying heavy oil, be 100 μ m or the following oil droplet of 100 μ m as long as this device can produce diameter. For example, can use the carousel-type device, drive nozzle type device, or two-fluid spray nozzle type device. The carousel-type device is that raw material is offered the dish of High Rotation Speed and makes the raw material scattering produce a kind of device of particle by centrifugal force. Usually, the diameter of this dish is 10-35cm and at 3,000-20, rotates under the speed of 000rpm. Drive nozzle type device is for the raw material pressurization and causes that raw material is the device of particle form from the spray orifice ejection of nozzle. Usually, expulsion pressure is about 20-700kg/cm2G and injection diameter are 0.3-5mm. Two-fluid spray nozzle type device is the theory according to injector, uses the gas injection stream to produce a kind of device of the materials flow of raw material. Usually, gas pressure is about 2-8kg/cm2G and feed pressure are about 1-5kg/cm2·G。
Although anyly in these injection apparatus can be used for the present invention, carousel-type and two-fluid spray nozzle type, especially the two-fluid spray nozzle type is preferred, when needing the drop of small particle diameter. When using two-fluid spray nozzle type device, nitrogen, helium, argon gas, air, carbon dioxide or similar gas can use separately or use as the mixture of two or more gases. Consider that from cost and safety air or nitrogen are preferred, nitrogen is particularly preferred.
Be 100 μ m or the tiny oil droplet below the 100 μ m in order to use these injection apparatus to produce particle diameter from heavy oil, heavy oil need to be remained liquid form. Without any restriction, needing only oil is liquid to oil viscosity. In general, oil preferably uses at 10 pools or the viscosity below 10 pools in 20 pools or the viscosity below 20 pools, and this depends on type, structure and the performance of institute's use injection apparatus.
Solid heavy oil can heat or make its liquefaction or adjusting viscosity with organic solvent diluting.
Injection method has a shortcoming, because it does not need to make water, this is opposite with the membrane emulsification method with the above-mentioned emulsion method. Do not make water mean the processing of having avoided waste water.
By in the said method any one, can easily make the material that size is not more than little shape of 100 μ m, such as particle, powder or fiber. Say that at random if the material of little shape contains a large amount of sizes less than the material of imperceptible little shape of 0.1 μ m, this class material is not suitable for the present invention, when considering the post processing of above-mentioned filtration step, stabilizing step and carburising step. The size of the material of the little shape that is obtained by said method fortunately, is usually greater than 0.1 μ m.
More than, as indicated, as if method (c), (d) or (e) only can be applicable to that softening point is lower than 45 ℃ initiation material or be the heavy oil of liquid at normal temperatures, but can find out, even softening point is not less than 45 ℃ pitch and also can be used in method (c), (d) or (e), if initiation material regulates softening point through preliminary treatment or viscosity satisfies above-mentioned requirements.
Second step
Second step of the present invention is that to make the material of little shape be that particle, powder or fiber have be suitable for the carrying out stabilizing step i.e. performance in the 3rd step. That is the oxidation of pitch air atmosphere that the cracked fuel oil of, originating from oil obtains is to begin under the temperature between 140-160 ℃. Therefore, if will stable material have and be lower than 160 ℃ softening point, be difficult to make material settling out, because material fusing or merge in the processing procedure of carrying out for stable operation. Therefore, necessary is, will be stable material should have and enough be higher than 140-160 ℃ softening point. Will be stable material should have at least to be higher than 180 ℃ softening point and preferably should to have and be higher than 200 ℃ softening point. Similarly, when material when being heated to the loss in weight that demonstrates after 300 ℃ greater than 5wt%, the problem that in the processing procedure of carrying out for the stable operation of material, also can melt or merge. The use of this class material is not preferred, also because this class material will discharge a large amount of volatile organic matters in processing procedure. Consider from safety perspective, should avoid the release of a large amount of volatile organic matters. So necessary is, material to be processed through being heated to the loss in weight after 300 ℃ and should remaining on below the 5wt% and preferably below 3wt%.
For this reason, in second step, extract light component by the material from little shape of the first step, making with an organic solvent. As the extraction use solvent, be necessary to use a kind of solvent, it general at least the material of little shape of 10wt% be left insoluble component, namely be retained in solid-state. In other words, extraction should be partly to extract those of light component (maximum 90wt%) with solvent. When using those solvents than above regulation that the solvent of high-solvency is more arranged, the productive rate of needed high softening point bitumen can reduce and usually cause the solution extraction effect (destraction) of the material of little shape of preparing in the first step, with thereby, the extraction with so strong solvability is inappropriate with the use of solvent.
As the organic solvent that satisfies above-mentioned requirements, can enumerate aliphatic hydrocarbon, ketone, and alcohols. As aliphatic hydrocarbon, can enumerate pentane, pentamethylene, n-hexane, isohexane, cyclohexane, normal heptane, isooctane, etc.; As ketone, can enumerate acetone, methyl ethyl ketone (MEK), metacetone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK) (MIBK), etc.; With as alcohols, can enumerate methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol (IPA), n-butanol, sec-butyl alcohol (SBA), n-amyl alcohol, n-hexyl alcohol, cyclohexanol, etc. Each of these solvents can be used separately or they can mix to regulate solvability, if necessary.
At random say, if the first step undertaken by emulsion process or film emulsification method, with the independent use of the immiscible solvent of water such as aliphatic hydrocarbon be not preferred because with the immiscible solvent of water when mixing with aqueous emulsion, can cause forming scum silica frost shape material. Scum silica frost shape material is difficult to by filtering or centrifugal the separation. Therefore, in this case, the alcohols that dissolves each other with water or the use of ketone are preferred. Similarly, can use aliphatic hydrocarbon and other alcohols or the mixture of ketone, when mixture and water dissolve each other.
Without any restriction, and can use any known method to the method for extraction light component. In the method for the invention, because raw material has been configured as the material that size is no more than little shape of 100 μ m, can finish rapidly the extraction operation, for example, allow the material of little shape mix with organic solvent with extraction, then by filtering or centrifugal recovery insoluble substance. When extracting processing, extraction is several times to tens times (by weight) that at random is selected from processed material (being the material of little shape) with the amount of solvent. If extraction is too little with the consumption of solvent, even asphalt material still can not have sufficiently high softening point after processing, because only can extract limited amount light component. In addition, when the material of little shape of granularity too little (namely less than 0.1 μ m) is processed, use a small amount of extraction solvent, the mixture of material and solvent has poor flowability and thereby is difficult to successfully extract operation. Therefore, preferably, use the extraction solvent of 3-30 times of consumption. Can at room temperature extract well, but in order to improve the solvability of solvent, can use higher temperature. Extraction time was finished fully extraction and is processed without limits and under regular situation in several hours. When the solvent of higher is used solvent as extraction, need long time to come the high softening point bitumen material of desolventizing or dry little shape. In this case, the preferred use, for example following operation sequence.
That is, at first, from the high softening point bitumen material of little shape, remove employed extractant well by filtration or similar approach; Secondly, use the high softening point bitumen material that lower solvability and more lower boiling this little shape of solvent wash are arranged than employed extractant; In order to remove high boiling extractant; Again, the material of dry little shape.
Certainly, the extraction operation is not limited to once, can repeatedly extract and drying process. By means of said method, can easily prepare a kind of softening point that is recorded by temperature gradient method and be higher than 180 ℃, preferably be higher than 200 ℃ and be lower than 5wt% through being heated to 300 ℃ of shown losses in weight that go out, preferably be lower than the high softening point bitumen material of little shape of 3wt%.
As above mentioned, has the softening temperature (recording) that is higher than 180 ℃ by temperature gradient method by the above-mentioned the first step and the second high softening point bitumen material that goes on foot the little shape that obtains.Softening temperature is identical with the bituminous softening temperature that is used for the spinning carbon fiber basically.Nonetheless, the high softening point bitumen of Huo Deing does not contain the BTX insoluble component in the present invention, and extremely low weight loss is arranged being heated to after 300.Therefore, the high softening point bitumen that obtains in the present invention is different from the pitch that is used for the spinning carbon fiber and thereby is unique product.Can reach a conclusion from above, the high softening point bitumen of Huo Deing has lower molecular weight and has narrower molecular weight distribution in the present invention.The high softening point bitumen of Huo Deing is the way preparation by the complete novelty different with usual way in the present invention.That is, the usual way of making high softening point bitumen comprises: thermal treatment at high temperature, subsequently pitch is made tiny particle.On the contrary, in the present invention, might be efficient and by means of a kind of method easily with the bituminous fine particle of industrial-scale production high softening-point, this method comprises: at first, make the fine particle of raw material heavy oil by specific method, then, secondly, allow the fine particle of raw material heavy oil improve softening temperature through specific processing.Therefore, in the first step of the present invention with in second step, do not need to use high temperature (as more than 350 ℃) thermal treatment fully, instant heating polymerization procedure, or catalyzed polymerization step (it is an indispensable step in the usual way).Because need not use thermopolymerization step or catalyzed polymerization step in the present invention, the high softening point bitumen that can obtain does not in the present invention contain optically anisotropic part.As above mentioned, the high softening point bitumen of Huo Deing is unique product in the present invention, because it has quite high softening temperature, low molecular weight is arranged, and does not contain the BTX insoluble component and is isotropic pitch fully.The special performance that it is believed that the high softening point bitumen that obtains in the present invention is the reason that sharply forms a large amount of apertures that uniform-dimension is arranged in the carburising step of narrating below.
The 3rd step
The 3rd step of the present invention comprises: the high softening point bitumen material of the little shape of heating and the material of oxidation acquisition stabilization in addition in oxygen containing atmosphere, this material is stabilized to a kind of like this degree, promptly can not take place to melt or merge when heating in the step (i.e. the 6th step or the 7th step) below.
Though the high softening point bitumen material of the little shape that obtains in second step of the present invention does not contain the component that is insoluble to the BTX solvent, if heat temperature raising gradually in oxygen-containing atmosphere (for example air), pitch is approximately being gained in weight because of oxidizing reaction (promptly having introduced oxygen) under 140-160 ℃.Along with the increase of weight, produce the component that is insoluble to the BTX solvent or is insoluble to quinoline.Even pitch has been transformed into the BTX insolubles of 100wt%, if but pitch also is not transformed into the quinoline insolubles of 100wt%, can cause problem when this class bituminous uses still in the step of back heating so, as distortion that causes because of fusing or fusion or the formation of disturbing hole.According to our understanding, in carburising step subsequently, be not melted cause point that shape changes and the quinoline non-soluble components contents reaches 100wt% in the material of stabilization point much at one.Specifically, pitch does not melt this point or the point of the desired lowest term of fusion corresponding to having met.Maximum yield after the carbonization is also realized in this point.Satisfy and be called the best stabilized condition below the stable condition of these requirements.
Therefore, the processing in the 3rd step should be harsher than best stabilized condition, and the best stabilized condition is that BTX insoluble component and quinoline non-soluble component all are the condition of 100wt% basically.To making the stable method of pitch not have specific restriction, as long as pitch is introduced oxygen through heating in oxygen-containing atmosphere.The treatment condition of this process change according to oxygen concn in the atmosphere.For example, under the situation about in air, handling, kept about 0.1-10 hour down at 250-400 ℃ with the speed elevated temperature of 0.1-10 ℃/min and pitch.
If handle under these conditions, can obtain the material of the little shape of asphaltic base of particle, powder or fiber shape, this material has been stabilized to a kind of like this degree, their not fusions or fusing when promptly heating in the step of back.
The stabilization material that obtains in the 3rd step of the present invention, can observe only has specific surface area long-pending corresponding to the appearance of particle, powder or fiber, and irrelevant with stable condition.This shows, reacting completely of taking place in the 3rd step is different from the common activation treatment (wherein producing hole) in oxidizing atmosphere.In this stabilizing step, do not produce hole.
If resulting stabilization material is in addition carbonization in statu quo, can obtain aperture and big specific surface area, diameter is the porous carbon material of following particle, powder or fiber shape of 100 μ m or 100 μ m.The carbonization condition with in the 7th step, make those conditions (below will go through) of the molded article carbonization of stabilization the same.
Though these carbonization conditions can be suitable and arbitrariness ground from known conditions, select, if use inert atmosphere conditions, can obtain to have narrow size-grade distribution, especially be rich in the porousness pitch base carbon material of micropore.And if in oxidizing gas atmosphere, carry out carbonization, can obtain to be rich in porous carbon material aperture, that have high specific surface area short period of time.So each condition has the characteristics of itself.
In order to make the molded article of ball shape, little granular, bar-shaped or sheet form, filler and shaping operation that the stabilization material that obtains in the 3rd step is used as molded article are to carry out according to the schedule of operation in the step of the 4th step and back.
In this case, the stabilization material that in the 3rd step, obtains can be under the condition identical with the 7th those conditions in going on foot that below will describe in addition carbonization in statu quo, perhaps by following will describe make the stable excess processes method of pitch be transformed into the material of excessive stabilization after in addition carbonization again.Much less, the material of the excessive stabilization that obtains by excess processes and also can be used as filler of the present invention from the material of the carbonization of its acquisition.Yet, in not significantly difference on final hole formation condition between the situation of the situation of using stabilization material and overuse stabilization material or its char-forming material, if molded article is transformed into the state of excessive stabilization in the 6th step.So in view of the reason of conserve energy, the use of stabilization material is more favourable.
The 4th step
The 4th step of the present invention is the step of producing shaping raw material, this raw material has comprised stabilization filler and the high softening point bitumen (as binding agent) that obtains according to those schedule of operation identical operations programs in going on foot with the present invention second, and wherein the amount of high softening point bitumen is 20-70wt% in the total amount of stabilization filler and high softening point bitumen.
Specifically, produce shaping raw material by following acquisition: allow high softening point bitumen and stabilization filler mix, the BTX solvent is joined in this mixture dissolve high softening point bitumen, mediate resulting mixture, remove the BTX solvent, and drying composite.In addition, high softening point bitumen can be dissolved in the BTX solvent in advance and then this solution be joined in the stabilization filler.After mediating mixture, remove the BTX solvent, dry resulting mixture.
Though stabilization filler and high softening point bitumen also can carry out blend by dry method, be difficult to cause that by dry method binding agent sufficiently adheres on the filler, be 100 μ m or the following fine powder of 100 μ m because binding agent and filler all are diameters.If blend is inhomogeneous, resulting molded article is also inhomogeneous, and it can cause cracking or distortion in heat-processed subsequently.So,, should note guaranteeing enough blend effect uniformly if use dry method.On the other hand, if with BTX dissolution with solvents high softening point bitumen and carry out blend, blend is to be easy to and completely.Remove the BTX solvent by drying, can obtain a kind of shaping raw material that comprises the high softening point bitumen that uses as the binding agent that adheres to the stabilization filler.
The dissolving of high softening point bitumen in the BTX solvent, the mixing of filler and binding agent, removing and the drying of product of BTX solvent can be undertaken by mixing machine, drying machine and the similar devices that uses common equipment such as commercial sources to obtain.Do not need special equipment or device.
The consumption of the BTX solvent of dissolving high softening point bitumen is the 0.3-10 weight part preferably, for the high softening point bitumen of 1 weight part.If the consumption of BTX solvent is lower than this amount, the viscosity of the solution of high softening point bitumen in the BTX solvent is higher, needs high mechanical power to come this mixture of blending.Resulting blend is uneven sometimes.On the contrary, if use too much BTX solvent filler can be deposited in the binder solution, it also can cause uneven blend effect.Also have,, need a large amount of heats in order to remove the BTX solvent and to carry out drying.
With the consumption of the high softening point bitumen of stabilization filler blend be the 20-70wt% of stabilization filler and high softening point bitumen total amount, preferred 30-60wt%.If the consumption of high softening point bitumen is lower than 20wt%, the intensity of goods is low after shaping, stabilization treatment and carbonization, like this, the fracture of product can take place when operation.On the contrary, if the consumption of high softening point bitumen is higher than 70wt%, molded article is inner can be melted and swelling, causes the molded article distortion.
Shaping raw material can contain aggregate, and this depends on the amount of the high softening point bitumen of institute's blend, the amount of BTX solvent, or employed mixing machine, kneader or moisture eliminator.These aggregates can disturb shaping operation as adding mould, and the homogeneity of the influence raw material of having filled.Preferably raw material should be pulverized before being shaped to molded article or be broken.
The 5th step
The 5th step of the present invention is that to be shaped as a kind of size, diameter or thickness be 10mm or the molded article below the 10mm such as ball material, pellet, bar or sheet stock for the raw material that will the 4th obtains in the step.The pressure forming method, when adding the BTX solvent granulation and after granulation the exsiccant method, or extrusion method can both be used as manufacturing process.
Because the shaping raw material that obtains in the 4th step is the material that comprises the binding agent that adheres to filler, can easily prepare molded article by the pressure forming method of only raw material being exerted pressure.Can use common molding condition.For example, it is in the following mould of 10mm or 10mm that the shaping raw material of predetermined amount is loaded into diameter, applies 0.1 ton/centimetre by piston or jumper bar 2To several tons/centimetres 2Pressure.Because binding agent adheres to filler fully, about 1.0 tons/centimetre 2Or 1.0 tons/centimetre 2Following pressure is just enough usually.The forming temperature of raw material can be near room temperature.Though raw material can heat, expectability obtains good effect by heating not under the temperature that is lower than binding agent softening temperature (normally 180 ℃ or higher), because be heated to these binding agent is flowed.
And, also might need not to use a mouthful mould, obtain pellet by means of granulating method.Because high softening point bitumen (it is a binding agent) dissolves in BTX solvent of the present invention, the BTX solvent can be used as the needed thinner of granulation.For example, the filler of stabilization and high softening point bitumen are dropped in the carousel-type pelletizer, then rotation pelletizer and might carry out granulation when adding the BTX solvent gradually.This method does not need to use the needed binding agent of granulation, because high softening point bitumen is as the binding agent in the granulation operating process.High softening point bitumen also can be used as the binding agent of the pellet of being produced, when BTX removes by drying.Also have, also might produce slurry from the filler of high softening point bitumen and stabilization, and make molded article from slurry by extrusion molding by adding the BTX solvent.Under the situation of the granulation of using the BTX solvent or extrusion method, can carry out the operation in the 4th step of the present invention and the 5th step simultaneously.
Significantly, size, diameter or the thickness of the molded article that obtains in the 5th step should be 10mm or below the 10mm.Specifically, the shortest distance of the outside surface from the center to the molded article must be 5mm or below the 5mm.If the size of molded article, diameter or thickness greater than 10mm, are difficult to the inside of stable formation goods in making the stable subsequent step of molded article.If the inside of molded article is not stablized fully, fusing or distortion can take place in carbonization process, a part of material is stayed the inside of molded article and can not produced aperture, thereby makes resulting molded article not have uniform hole.The size of these molded articles and intensity can be by suitably selecting high softening point bitumen the introducing amount or the consumption of BTX solvent regulate.
The 6th step
The 6th step in the methods of the invention is the step that is stabilized in the molded article that in five step make by handling in oxygen-containing atmosphere, specifically, is used for stablizing simultaneously, preferred filler part and the binding agent part excessively stablized.
Generally, in order to make the asphalt base carbon fiber with sufficient intensity, the stabilization condition should preferably be regulated fully to obtain BTX insoluble component and the quinoline non-soluble component of 100wt% basically in the material of resulting stabilization.Specifically, these conditions are with the same in the best stabilized condition of being discussed about the 3rd step.
Yet, be used for stablizing the bituminous condition should surmount the needed best stabilized condition of binding agent from the same manner of being mentioned the narration in the 3rd step those selections here.If binding agent part by stabilization fully, can not expand or be out of shape in carbonization process.Also have, formed hole trends towards to heterogeneous, this owing in inertia or oxidizing gas atmosphere filler part and binding agent partly on the difference of reactive behavior.
Carbonization therein is under the situation of the present invention of carrying out in inert atmosphere, if the material of the stabilization of being produced by the best stabilized condition was carbonized in the 7th step of back, the specific surface area of resulting char-forming material reduces inevitably, if carbonization temperature is below or above very narrow temperature range 600-800 ℃.Meanwhile, oxygen concn still trends towards improving under the best stabilized condition in the material of stabilization, when employing with regard to temperature and treatment time when more exacting terms makes the excessive stabilization of material than the best stabilized condition, oxygen concn almost becomes constant in the material of resulting stabilization, although the productive rate of the material of stabilization descends gradually.When the material of the excessive stabilization that reaches capacity when oxygen concn wherein was carbonized, the oxygen that is adsorbed began to discharge under 500 ℃ or higher temperature, produces a large amount of holes simultaneously.Resulting material has enough big specific surface area and this bigger serface and remains to 1,100 ℃ high temperature always.
So, in wide carbonization temperature scope by handle obtaining the molded article of enough big specific surface area, preferably, this material should be stabilized under exacting terms more in the 6th goes on foot, rather than under the best stabilized condition.Specifically, this type of condition should be than harsher in order to make BTX solvent insoluble component and quinoline non-soluble component be essentially the 100wt% conditions needed, preferably, this condition should be enough harshness so that in the material of handling oxygen concn reach capacity, thereby make filler part and binding agent part by excessive stabilization simultaneously.
Stabilization method is had no particular limits.Can use almost and in the 3rd step of the present invention, be the same condition of those conditions that material settling out adopted of little shape of making high softening point bitumen.Specifically, this material is heated to 250-400 ℃ temperature with the heat-up rate of 0.1-10 ℃/min and kept about 0.1-10 hour under this temperature in air atmosphere.Can make the excessive stabilization of material by the Heating temperature and the retention time of regulating under these conditions.
For the molded article of the stabilization that in the 6th step of the present invention, obtains or the molded article of excessive stabilization, only can observe corresponding to specific surface area as the outer surface area of particulate material, powder material or the fiber material of shaping raw material, and with the conditional independence of molded article stabilization.This shows makes this stable step of pitch not produce hole.
Also wish to select these excessive exacting terms to come the stable formation goods, in carburising step subsequently, form tarry matters so that prevent.
The 7th step
The 7th step of the present invention is the step that makes material (i.e. the stabilized molded article or the material of little shape in the 3rd step or the 6th step) carbonization.Carbonization is operated or is carried out in inert atmosphere or in oxidizing gas atmosphere.Below explain in detail each method.
The carbonization operation of carrying out in inert atmosphere at first is described.Can use the usual way of carrying out carbonization by heating in inert atmosphere.Carbonization temperature basis, material stabilized condition in the 3rd step of as above mentioning or the 6th step changes.When material was stabilized under top condition, the carbonization temperature in 600-800 ℃ of scope was suitable for, still, when material than the best stabilized condition more under the exacting terms when stabilized, this carbonization temperature scope is 500-1,100 ℃.In the method for the invention, in these temperature ranges, can obtain to have the product of bigger serface, the product of a large amount of holes is promptly arranged by carbonization.
For example, when (wherein this carbonated product is to make from the petroleum naphtha pressure tar as starting raw material by following process: according to three steps of the first step to the by carbonated product under liquid nitrogen temperature by the BET method, or according to the material or the molded article of little shape of the excessive stabilization of the first step to the six step preparation, with the heating of the heat-up rate of 10 ℃/min and in nitrogen atmosphere its was kept 1 hour then and makes material or goods carbonization) on nitrogen when adsorbing to come measurement the specific area, product for carbonization under 400 ℃ of temperature is only observed little specific surface area, and when carrying out carbonization under 500 ℃ at only high 100 ℃, can obtain the product of big specific surface area than 400 ℃; And when carbonization temperature when being 1,100 ℃ this product still demonstrate big specific surface area, still,, only observe little specific surface area in resulting carbonated product when carbonization temperature only raises 100 ℃ to 1,200 ℃ the time.By same mode, under the situation of the unsaturated stabilization material of oxygen concn, only in 600-800 ℃ limiting temperature scope, obtain big specific surface area therein.These facts show, the generation of hole and destruction are extremely violent in the method for the invention, and the slight variation of carbonization condition makes specific surface area that big variation take place, and has shown the extreme homogeneity in porous carbon materials (being the material of molded article of the present invention or little shape) mesoporosity.
The generation of hole and destruction are to be adsorbed by the nitrogen under the liquid nitrogen temperature to judge that even without adsorption of nitrogen, this does not deny the existence of micropore in the present invention, and micropore is so little so that there is not nitrogen molecule to enter.For example, variation by pore dimension causes when carbonization temperature is considered to from the acute variation of 1,100 ℃ of above-mentioned specific surface area that is taken place when being increased to 1,200 ℃.Specifically, nearly all " hole that size can allow nitrogen enter " that exists when carbonization temperature is 1,100 ℃ is transformed into " hole that size can't allow nitrogen enter " when carbonization temperature is increased to 1,200 ℃.
Other carbonization condition except the carbonization temperature in the 7th step as heat-up rate and soaking time, can be selected in normally used scope.Usually know, temperature rising speed, promptly heat-up rate can be decided according to the type of employed carbide furnace.Specifically, when using the batch-type carbide furnace, temperature rising speed is about 1 ℃/min-100 ℃/min, and is about 10 ℃/min-1 when use successive type carbide furnace, 000 ℃/min.Soaking time is about 1 minute-10 hours.
By the porous carbon material of the inventive method acquisition or the specific surface area of molded article, record by the nitrogen absorption of BET method under liquid nitrogen temperature, be 300m 2/ g or higher.When by Horvath-Kawazoe method (HK method) when the nitrogen adsorption isothermal curve is analyzed, nearly all hole has the diameter that is lower than 10 dusts.
Porous carbon materials or the molded article with having uniform micro be made up of uniform carbon can be made by method of the present invention under condition discussed above easily and efficiently.
Then, will be described in detail in the method for carrying out carbonization in the oxidizing gas atmosphere below.
When needs production diameter was the porous carbon materials of 100 μ m or particle, powder or fiber shape below the 100 μ m, the stabilization material of the little shape that obtains in the 3rd step was carbonized.When needs production porousness forming carbon goods, the molded article of the stabilization that obtains in the 6th step is carbonized.
At least a oxidizing gas that is selected from carbonic acid gas and steam is used for activated carbon material.Though can use other oxidizing gas well known in the prior art, when the easy degree from aftertreatment and off gas treatment considers that carbonic acid gas and steam are preferred.When comparing these two kinds of gases, comparatively fast some also produce bigger hole to the general known response of steam, and the known aperture that more is easy to generate of carbonic acid gas, although speed of reaction is low.Yet under situation of the present invention, though steam provides fast slightly speed of reaction, the pore dimension of resulting porous carbon material does not have too big difference between the situation of the situation of using steam and use carbonic acid gas.
When in inert gas atmosphere such as nitrogen, carrying out carbonization, restricted to the specific surface area of resulting porous carbon material, although can obtain to be rich in the carbon material of micropore.Even under the high temperature of 900 ℃ or 1,000 ℃ by using inert gas atmosphere still can not obtain and the same big specific surface area of specific surface area by the carbonization acquisition in oxidizing gas atmosphere.Reason is considered to, and in the carbonization process that carries out in inert atmosphere, has only in the material of introducing stabilization Sauerstoffatom with CO, CO 2, H 2When discharging, the form of O and similar gas produces hole, and in the carbonization process in oxidizing gas atmosphere, not only by discharging these CO, CO 2And H 2O, and by discharging the CO that reaction produced by the stabilization material of the Sauerstoffatom in the oxidizing gas atmosphere and the carbonization of wanting, CO 2And H 2O produces hole.
Under the condition of from the known conditions of prior art, selecting, can carry out carbonization by using common equipment.Change though these conditions wait according to the concentration of target specific surface area, employed oxidizing gas, the carbonization 800-1 that is everlasting most carried out under 100 ℃ the temperature about 1 minute-15 hours.
For example, when being carbonized in the carbon dioxide atmosphere of stabilization material that obtains by method of the present invention 100%, handling ten or several hrs under 800 ℃ the temperature or all can to obtain specific surface area below 10 minutes or 10 minutes be 2 handling under 1,100 ℃ the temperature, 000m 2/ g or bigger porous carbon materials are adsorbed by nitrogen according to the Langmuir method and to measure.
Because the stabilization material that obtains in the 3rd step or the 6th step contains the oxygen of a large amount of introducings, this material produces the waste gas that contains carbonic acid gas when heating under 400-600 ℃.Because this temperature range is starkly lower than the temperature range that the priming reaction of carbonic acid gas can carry out, the carbonic acid gas that contains in waste gas is used as oxidizing gas, if this gas is recovered and is circulated in the carbonization process.
Can obtain specific surface area by method of the present invention is 3,000m 2/ g or higher carbon material are adsorbed by nitrogen according to the Langmuir method and to measure.Certainly, if the condition of suitable this method of selection can obtain the material of less specific surface area.The porous carbon materials that is obtained by the present invention has full-blown therein aperture and generally demonstrates pore distribution extremely uniformly, with common gac Comparatively speaking.
In general, according to the size of bore dia, aperture is divided into " micropore " that diameter is lower than 20 dusts, and diameter is that " mesopore " and the diameter of 20-500 dust is 500 dusts or above " macropore " of 500 dusts.(wherein P is at the adsorption equilibrium pressure of measuring nitrogen under the temperature to relative pressure P/Ps corresponding with the aperture of diameter 20 dusts when measuring, with Ps be at the saturated vapour pressure of measuring nitrogen under the temperature), adsorption isothermal curve by the nitrogen of Dollimore-Heal method (DH method) under the liquid nitrogen temperature records, and is P/Ps=0.09.Then; suppose that the value when P/Ps=1 is the whole loading capacity of nitrogen; microporosity (vol%); it be when P/Ps be 0.09 or 0.09 the per-cent of nitrogen loading capacity (diameter is the capacity of 20 dusts or the hole below 20 dusts) and whole loading capacity when following; the microporosity that shows the porous carbon material of in carbonizing treatment, being produced by method of the present invention by use oxidizing gas atmosphere; for specific surface area is 1,500m 2/ g or 1,500m 2The following material of/g is 95% or higher, is 2 for specific surface area, 200m 2/ g or 2,200m 2The following material of/g is 90% or higher, is 3 for specific surface area, 000m 2/ g or 3,000m 2The following material of/g is 70% or higher.Specific surface area is about 3,000m 2The loading capacity of the carbon material of/g is calculated according to the method (P/Ps=0.44 or lower) the same with diameter 40 dusts or the hole below 40 dusts, is 90% or higher.
Though also do not understand the reason of main these apertures of generation at present, the homogeneous reaction of high softening point bitumen that produce, that have even composition and narrow molecular weight distributions and stable operation in the 3rd step and the 6th step is considered to produce the reason of aperture in second step of the present invention.
Be under the situation of material of little shape of particle, powder or fiber shape at product and product is under the situation of molded article, the hole forms condition, specific surface area is nearly all the same with pore size distribution.This filler part and binding agent that shows molded article partly all is made up of uniform carbon.The hardness that molded article had is enough to resist finger pressure and is not broken, even specific surface area is higher than 3, and 000m 2/ g.
The employed stove of carbonization can with mention already the same, therefore, further explain it is unwanted.
In general, also there is not to set up the method for accurately measuring the little aperture seen in the carbon material of producing in the method for the invention and (with respect to 20 dusts or this little aperture below 20 dusts) pore size distribution so far.The value of measuring is according to noticeable changes such as measuring method, analytical procedures.So, should estimate these micropores particularly according to the practical application of product.In practice, estimate hole by means of specific analytical technology from the characterization of adsorption (molecular dimension: major diameter=4.1 dusts, minor axis diameter=3.0 dusts, the open No. flat 4 (1992)-13288 of Japanese Patent) of nitrogen.Can judge that according in manufacture method with the various variations on creating conditions, this evaluation method is enough to determine the fundamental characteristics of material or the variation on these characteristics.
Just as described above, the porous carbon material of foraminate particle, powder or fiber shape, perhaps the molded article of porous carbon material can easily be obtained by method of the present invention.
In addition, possible carbon material without any hole made according to the method for the present invention, or the molded article of this carbon material.On this meaning, the invention provides " porosity control method ", have a mind to control the generation of uniform small pores.
Can efficiently produce the porous carbon material of uniform small pores with technical scale from the starting raw material of cheapness such as heavy oil or from its low softening point asphalt that makes by method of the present invention, this material can be used as the absorption-desorption agent, molecular adsorbent, catalyzer, electrode carbon material and analogue.Because starting raw material such as heavy oil are made into the material of little shape in the method for the invention,, thereby can overcome existing various economy and technical problem in the prior art that is used for making high softening point bitumen then through handle improving its softening temperature.
Also have,, might make molded article, and it is not acquisition in the prior art by porousness carbon uniform small pores, that forms by even carbon because the filler and the binding agent that obtain from identical starting raw material are used to make molded article.
In addition, in usual way, but do not need to use in the method for the invention, make and to avoid cleaning product and the complex operations that reclaims chemical after handling for production has a large amount of activating chemical product that need of product of big specific surface area.
To at length explain the present invention with reference to the following examples, but these embodiment must not think the scope of the present invention that limited.
Hereinafter, " % " refers to " wt% ", if do not stipulate in addition.
Embodiment 1
Having prepared softening temperature by the vacuum distilling of heavy oil is the low softening point asphalt of 71 ℃ (being measured by temperature gradient method), and this heavy oil is the by product (petroleum naphtha pressure tar) that alkene is made in the petroleum naphtha cracking.This bituminous productive rate based on the petroleum naphtha pressure tar is 73%.Bituminous dimethylbenzene insolubles content is 0%, and quinoline insolubles content is 0%, and loss in weight on heating is 17.9% (being recorded by thermo-balance) when being heated to 300 ℃, and results of elemental analyses: C:92.9%, H:7.0%, S:0.02% and H/C atomic ratio are 0.90.
The melt spinning device of the nozzle of diameter (D) 0.25mm and length (L) 0.75mm (L/D is than=3) is equipped with this pitch input, at 135 ℃ temperature and 5Kg/cm 2Spinning under the top hole pressure of G is drawn by the air extractor that is contained in the nozzle below then and is dialled, and obtaining Fibre diameter is the fiber of the low softening point asphalt of 20 μ m.
The fiber of this low softening point asphalt of 200g is put into 4, and in the acetone of 000ml and SBA (acetone/SBA volume ratio=20/80) mixed solvent, mixture was by magnetic stirrer 1 hour.This mixture filters by the G-4 glass filter then.Resulting insoluble component is put to 4, also stirs once more 1 hour in the solvent of the fresh mix of 000ml.Mixture filters by same glass filter, resistates methanol wash 3 times.Obtain solid product, drop in the vacuum drier, then 30 ℃ dry 5 hours down, obtain to have removed the high softening point bitumen of light constituent.
This bituminous productive rate based on the fiber of low softening point asphalt is 58%.Pitch has 216 ℃ of softening temperatures (being recorded by temperature gradient method), and the dimethylbenzene insolubles is 0%, and quinoline insolubles is 0%, loss in weight on heating when being heated to 300 ℃ is 2.1%, and results of elemental analyses is: C:92.8%, H:7.1%, S:0.03% and H/C atomic ratio are 0.91.By using scanning electronic microscope (SEM) to observe this high softening point bitumen, confirmed this be cut into the long but Fibre diameter of tens μ m almost with extraction before the same fibrous powder.
Then, this powder of high softening point bitumen heat-up rate with 0.5 ℃/min in air heats, and by allowing its under temperature 195-355 ℃ of regulation, keep being stablized in 1 hour.Resulting stabilization material kept 1 hour down with the heat-up rate heating of 10 ℃/min and at 1,000 ℃ in nitrogen gas stream, thereby made the material carbonization of stabilization.The productive rate of stabilization material and performance, the productive rate and the outward appearance of char-forming material are listed in the table 1.Two productive rates are all based on the high softening point bitumen after the extraction light constituent.
Show in the table that stabilized high softening point bitumen melts under 215 ℃ the temperature not being higher than in carbonization process.Kept the shape of fiber at the pitch of 235 ℃ of following stabilizations, but fiber bonds together the formation aggregate mutually.Making the stable minimum temperature of pitch is 255 ℃, makes not melt in carbonization process or bond.When fibre strength was quite important, this was the best stabilized condition.
Can recognize that the changes of properties of resulting stabilization material has shown such fact from table, although the quinoline non-soluble component just reaches 100% when pitch is stabilized under the best stabilized condition, oxygen concn is still improving.Can find out, when oxygen concn is increased to temperature always and reaches about 300 ℃, and almost saturated under 300 ℃ or higher temperature.
Secondly, for resulting carbonated product, according to ASTM standard (Draft Proposal 7-18-76, Revision 2 4-6-81), use direct reading out type surface-area survey meter, MONOSORB (trade(brand)name), model: MS-8 (being made by QUANTACHROME company) is by the nitrogen adsorptive capacity measurement the specific area of BET method (SA (BET)) under the liquid nitrogen temperature.The results are shown in table 1, wherein shown, though under best stabilized condition (255 ℃), only observe little specific surface area and almost do not adsorbed the hole of nitrogen, but, when at high temperature, promptly when more allowing pitch excessively stablize under the exacting terms (more than 295 ℃ or 295 ℃) for needed those conditions that reach capacity, can observe big specific surface area, illustrate to have formed aperture than oxygen concn.
And, for the char-forming material that under the stabilization temperature of 255 ℃ and 355 ℃, obtains, use the adsorption isothermal line survey meter, BELSORP (trade(brand)name), model: 28SA (making) by Japanese Bell Co., by measuring the adsorption isothermal line under the liquid nitrogen temperature, by Langmuir method (SA (Lang)) measurement the specific area.The result also is shown in table 1.When stabilization temperature is 255 ℃, be 1m from the specific surface area of adsorption isotherm line computation 2/ g.This numerical value is almost with the same from the outer surface area of the outside diameter of fiber and length measurment, reconfirm when pitch stable under the best stabilized condition and during 1,000 ℃ of following carbonization, almost do not produce the aperture of adsorbable nitrogen.When pitch is stabilized, confirmed 688m under 355 ℃ of temperature 2The high numerical value of the specific surface area of/g.
These specific surface area values that obtained by the Langmuir method are different from the value that is recorded by the BET method of using MONOSORB.It is apparent that in the measurement of the specific surface area of aperture the result is subjected to the difference of measuring method greatly and is being used for the influence of the difference in the theoretical calculation formula of measurement the specific area.Though judging two kinds of methods all can accept to be used for confirming that effect of the present invention, BET method are mainly used in embodiment and carry out some mensuration by the Langmuir method.
The specific surface area of stabilization material is about 0.2-0.4m before carbonization in all cases 2/ g, almost be with from the diameter of fiber and the same value of outer surface area of length computation, and be used for stablizing bituminous conditional independence, illustrate when pitch is stabilized, not form hole.
For the char-forming material that makes from 355 ℃ of following stable pitches, the absorption-desorption isothermal curve of nitrogen is shown in Fig. 1 under liquid nitrogen temperature.In Fig. 1, transverse axis represents that P/Ps and Z-axis represent the adsorptive capacity of nitrogen.This figure shows that it is low-down zone that absorption almost completely occurs in relative pressure P/Ps (P: the adsorption equilibrium pressure of nitrogen under the measurement temperature, Ps: at the saturated vapor pressure of measuring nitrogen under the temperature), and the aperture that extremely narrow diameter Distribution is arranged is described in char-forming material.
Also have, in Fig. 1, when absorption, observe some hysteresis phenomenon in the thermoisopleth of (stain) during in the thermoisopleth of (circle) with in desorb.Hysteresis is usually an observed phenomenon when measuring aperture.Though the reason of this phenomenon does not understand that also this does not deny the existence of uniform small pores.
By Horvath-Kawazoe method (HK method) from these data computation pore size distributions.This carbon material is proved has uniform micropore, and extremely narrow pore size distribution and central aperture are arranged is about 6 dusts.
Table 1-a
Stabilization temperature (℃)
103 103 102 100 96 dimethylbenzene insolubles 69 100 100 100 100 (wt%) quinoline insolubles 0 33 75 100 100 (wt%) ultimate analyses (wt%) of 195 215 235 255 275 stabilization material productive rates (wt%)
C??????????????86.7???-????78.4???-???71.2
H??????????????6.2????-????4.5????-???3.1
(2) good SA (BET) (m is merged in O 7.1-17.1-25.7 carbon material productive rates (wt%)--63 64 60 outward appearances fusings (1) fusings (1) 2/ g)--0.2 0.3 5.8 SA (Lang) (m 2/ g)---0.4-(1): fusing when the stabilization pitch fibers is carbonized.(2): when the stabilization pitch fibers is carbonized, merge.
Table 1-b
Stabilization temperature (℃) 295 315 335 355 stabilization material productive rates (wt%), 91 90 82 77 dimethylbenzene insolubless----(wt%) quinoline insolubles (wt%)----ultimate analysis (wt%)
C???????????????-????69.5???-????68.5
H???????????????-????2.3????-????2.0
O-28.2-29.5 carbon material productive rate (wt%) 56 53 48 44 outward appearances are SA (BET) (m carefully 2/ g) 320 368 382 377 SA (Lang) (m 2/ g)---688
Embodiment 2
The diameter that use obtains in embodiment 1 is the low softening point asphalt fiber of 20 μ m, extracts according to the mode identical with embodiment 1, and methanol wash and drying, just Pentyl alcohol makes the fibrous powder of high softening point bitumen as extraction solvent.The productive rate of this powder is 51%, based on the low softening point asphalt fiber.The softening temperature of this powder is 232 ℃ (being recorded by temperature gradient method), dimethylbenzene insolubles content 0%, quinoline insolubles content 0%, as the loss in weight on heating 1.8% that is heated to 300 ℃, results of elemental analyses: C:92.8%, H:7.1%, S:0.02% and H/C atomic ratio 0.91.
This fibrous powder of high softening point bitumen is stablized by following: with 0.5 ℃/min heat-up rate heating and in air the temperature in regulation kept 1 hour down for 255 ℃, 305 ℃, 355 ℃ and 395 ℃, subsequently with the heating of the heat-up rate of 10 ℃/min and in stream of nitrogen gas in 1,000 ℃ keeps carrying out in 1 hour carbonization down, the performance of stabilization material and productive rate, and the productive rate of char-forming material, outward appearance and performance are shown in table 2.According to mode similar to Example 1, measure the specific surface area of resulting char-forming material by BET method (SA (BET)) and Langmuir method (SA (Lang)).
Under the situation of 1,000 ℃ carbonization temperature, the char-forming material that makes from a kind of stabilization material of handling under 255 ℃ temperature has little specific surface area, thereby does not have the aperture of adsorbable nitrogen.Demonstrate bigger specific surface area from the char-forming material that material obtained of those excessive stabilizations of under the comparatively high temps of 305 ℃, 355 ℃ and 395 ℃, handling, illustrate to have formed aperture.
Also have, very similar from adsorption isothermal curve and Fig. 1 of those char-forming materials that material obtained of stabilization under the temperature of 305 ℃ and 355 ℃.The isothermal curve that obtains in this embodiment shows, absorption almost completely occurs in relative pressure (P/Ps) lower the time.Confirmed that from the pore size distribution of these data computation carbon material has uniform micropore by the HK method, extremely narrow pore size distribution, central aperture are about 6 dusts.
Table 2
Stabilization temperature (℃)
255 305 355 395 stabilization material productive rates (1) (wt%) 103 93 77 36 dimethylbenzene insolubless 100---(wt%) quinoline insolubles 100---(wt%) ultimate analysis (wt%)
C??????????????????-?????68.2??67.7??-
H??????????????????-?????2.2???2.0???-
O-29.6 30.3-carbon material productive rate (wt%) 61 51 40 17 outward appearances are SA (BET) (m carefully 2/ g) 0.2 371 385 398 SA (Lang) (m 2/ g) 0.5 539 638-
(1): based on the productive rate of high softening point bitumen fiber
Embodiment 3
In embodiment 2 by thermal treatment under 355 ℃ temperature in addition excessive stabilization material heat-up rate with 10 ℃/min in nitrogen gas stream of obtaining of stabilization be heated to 400 ℃-1,500 ℃, and under predetermined temperature, keep carrying out in 1 hour carbonization.The ultimate analysis of char-forming material, specific surface area (SA (BET)) and specific surface area (SA (Lang)) are shown in table 3.
From this table, can understand, when carbonization temperature raise to surpass 400 ℃, form hole fast and hole disappears fast when surpassing 1,100 ℃ when carbonization temperature raises.
Can confirm that from the result who records adsorption isothermal line according to the mode identical all carbon materials that are carbonized are porous carbon materials, each have extremely narrow pore size distribution under the temperature in 600 ℃ of-1,100 ℃ of scopes with embodiment 1.In each of these carbon materials, central aperture is 6 dusts.
Table 3 carbonization temperature ultimate analysis (wt%) SA (BET) SA (Lan
g)(℃)?????????C??????H???????O?????(m 2/g)??(m 2/g)400????????70.2????2.11????27.8????2.2??????-500????????79.5????2.0?????18.4????373??????-600????????90.5????2.0?????7.5?????380?????753800????????96.5????0.6?????2.8?????390?????7741000???????99.4????0.2?????0.1?????385?????6381100???????99.8????0.1?????0.0?????329?????5531200???????-???????-???????-???????5.5??????-1300???????-???????-???????-???????0.8??????-1500???????-???????-???????-???????0.3??????-
Embodiment 4
In embodiment 2 by thermal treatment under 255 ℃ temperature in addition excessive stabilization material heat-up rate with 10 ℃/min in nitrogen gas stream of obtaining of stabilization be heated to 500 ℃-1,000 ℃, and under predetermined temperature, keep carrying out in 1 hour carbonization according to the mode identical with embodiment 2.In the carbonizing treatment process of stabilization material, become white and vaporific (from about 300 ℃) from the carbide furnace expellant gas, and meanwhile, brown or brownish black tarry matters sticks to the outlet of the heating tube that is positioned at stove.
Based on the productive rate of the carbon material of high softening point bitumen fiber, and specific surface area (SA (BET)) is shown in table 4.
Result from this table can find, when not being carbonized by the stabilization material of oxygen saturation (being that oxygen concn does not reach highest level), can in 600-800 ℃ of so narrow temperature range, form bigger specific surface area, but be below or above this scope, specific surface area descends fast.
Table 4 carbonization temperature productive rate SA (BET) (℃) (wt%) (m 2/ g) 500 71 59 600 66 328 800 63 297 900 62 185 1,000 61 0.2
Embodiment 5
Obtaining softening temperature by the petroleum naphtha pressure tar distillation that will use in embodiment 1 is the low softening point asphalt of 49 ℃ (being recorded by temperature gradient method).The solution for preparing low softening point asphalt by the dimethylbenzene that in the low softening point asphalt of 70 weight parts, adds 30 weight parts.By using nonionogenic tenside is polyoxyethylene nonylplenyl ether (Emulgen985, trade(brand)name, Kao Corp. manufacturing) 2% aqueous solution is as dispersion agent with by using by Ise Kagaku Co., Ltd. make, the film-type distributed test device as 4 μ m-micropore glass of dispersion medium is housed, make a kind of so-called O/W type emulsion of the low softening point asphalt solution of the dispersion form that contains 11% (by volume).That is, allow bituminous solution extrude, enter into dispersion agent and make emulsion by micropore glass.
Then, under agitation this emulsion is splashed among the SBA of 10 times of amounts gradually, with the dimethylbenzene and the soluble component that is contained in the low softening point asphalt of extraction dissolving usefulness.This mixture, promptly the suspension that so obtains comes the separate solid material through centrifugal treating, then, and the solid matter methanol wash, and dry.In addition, solid matter is stirred in the Pentyl alcohol of 20 times of amounts and filters.The filter cake methanol wash, dry then.Therefore obtain the micro-spherical particle of high softening point bitumen.With low softening point asphalt (being starting raw material) is that the productive rate of the micro-spherical particle of basic calculation is 48%.
So the high softening point bitumen that obtains has median size 16 μ m and has following character: the softening temperature that is recorded by temperature gradient method: 243 ℃; Dimethylbenzene insolubles: 0%; Quinoline insolubles: 0%; Be heated to 300 ℃ weight loss: 1.7%; Ultimate analysis: C:92.7%, H:7.1%, S:0.02%; H/C atomic ratio: 0.92.
Particle heats in air atmosphere with the heat-up rate of 0.5 ℃/min, by keeping being stablized in 1 hour at 355 ℃.So the particle of the stabilization that obtains is heated to 1,000 ℃ and kept 1 hour and be able to carbonization with the heat-up rate of 10 ℃/min under this temperature in nitrogen atmosphere.Therefore, obtain the carbon granule of microspheroidal.Based on the high softening point bitumen particle that is obtained by the Pentyl alcohol extraction treatment, the productive rate of stabilization particle and carbon granule is respectively 72% and 40%.The specific surface area of the carbon granule that is recorded by BET method (SA (BET)) is 375m 2/ g.
The comparative example 1
The H/C atomic ratio is that 0.70 coal tar is processed by thermal treatment, uses solvent to be separated, and according to usual way (USP5 for example, 091,072) carries out hydrogenation, obtain mesophase pitch (intermediate phase content: 99% (area), the softening temperature that records by temperature gradient method: 265 ℃ based on coal, dimethylbenzene insolubles: 96%, quinoline insolubles: 0.6%, be heated to 300 ℃ weight loss: 0.03%, ultimate analysis: C:93.8%, H:4.3%, H/C atomic ratio: 0.55).By using Han Xieer (Henschel) mixing machine that pitch is pulverized and being the powder of the high softening point bitumen of 21 μ m by 325 orders (JIS) the screen cloth acquisition median size of sieving.
By in air, keeping making in 5 hours the pitch stabilization down, in nitrogen atmosphere, keep in addition carbonization in 1 hour down subsequently in 1,100 ℃ with the heating of the heat-up rate of 0.5 ℃/min and temperature 320-360 ℃ of regulation.The character and the productive rate of stabilization material and char-forming material are shown in table 5.
The result of this table 5 shows, compares with the material of producing in the method for the invention, and material such as H/C atomic ratio are lower than 0.8 the mesophase pitch based on coal and only produce a spot of hole.
Table 5
Stabilization temperature (℃)
320 340 360 stabilization material productive rates (1)(wt%) 103 99 65 ultimate analyses (wt%)
C????????????????80.9???77.6???71.2
H????????????????2.3????2.0????1.7
O 15.9 19.5 25.9 carbon material productive rates (1)(wt%) 75 69 38 SA (BET) (m 2/ g) 17 20 37 SA (Lang) (m 2/ g)--37 (1): based on the productive rate of high softening point bitumen
The comparative example 2
Process by thermal treatment with employed identical coal tar in comparative example 1, use solvent to be separated, and according to usual way (USP4 for example, 925,547) carry out hydrogenation, acquisition is based on isotropic pitch (the intermediate phase content: 0% (area) of coal, the softening temperature that records by temperature gradient method: 215 ℃, dimethylbenzene insolubles: 59%, quinoline insolubles: 0%, be heated to 300 ℃ weight loss: 0.02%, ultimate analysis: C:93.3%, H:4.5%, H/C atomic ratio: 0.58).By using Han Xieer (Henschel) mixing machine that pitch is pulverized and sieving by 325 eye mesh screens that to obtain median size be the powder of the high softening point bitumen of 23 μ m.
According to the method identical with comparative example 1 with pitch stabilization and carbonization.The character and the productive rate of stabilization material and char-forming material are shown in table 6.
Hole as shown in table 6, that this isotropic pitch makes carbonated product have greater number, with those products of producing from comparative example 1 mesophase pitch Comparatively speaking.Yet this product has the low specific surface area of material that obtains than method of the present invention.
For reference, for the carbon material that in embodiment 1, comparative example 1 and comparative example 2, obtains, figure 2 illustrates based on the relation between the productive rate of the char-forming material of the high softening point bitumen before the stabilization and the specific surface area that records by use MONOSORB (trade(brand)name) by BET method (SA (BET)).In the accompanying drawings, is corresponding to obtaining the result in embodiment 1 ,+corresponding to the result who in comparative example 1, obtains and ◇ corresponding to the result who in comparative example 2, obtains.This accompanying drawing shows, under the bituminous situation that is obtained as the heat treating method in the comparative example by the common process method, can not obtain the carbonated product of big specific surface area even productive rate descends greatly.In addition, verified from embodiment and comparative example's data, big variation will take place according to employed raw material in the result who produces hole, though use same condition stablize they and carbonization they, and proof, method of the present invention produces the carbon material of uniform micro effectively.
Table 6
Stabilization temperature (℃)
320 340 360 stabilization material productive rates (1)(wt%) 103 96 47 ultimate analyses (wt%)
C?????????????79.9????74.7???68.5
H?????????????2.4?????2.0????1.7
O 16.6 22.1 27.8 carbon material productive rates (1)(wt%) 74 61 24SA (BET) (m 2/ g) 60 90 228SA (Lang) (m 2/ g)--325
(1): based on the productive rate of high softening point bitumen
The comparative example 3
By commodity mesophase pitch (the intermediate phase content: 100% (area) that uses the superpower acidity catalyzer to produce from naphthalene, the softening temperature that records by temperature gradient method: 240 ℃, dimethylbenzene insolubles: 88%, quinoline insolubles: 43%, be heated to 300 ℃ weight loss: 0.2%, ultimate analysis: C:94.5%, H:5.3%, H/C atomic ratio: 0.67) pulverize, and sieve by 325 eye mesh screens that to obtain median size be the powder of the high softening point bitumen of 22 μ m with the Han Xieer mixing machine.
In air, be heated to 320 ℃ and under this temperature, keep making in 5 hours the pitch stabilization with the heat-up rate of 0.5 ℃/min.The productive rate of stabilization material is 103%, the result of ultimate analysis: C:74.5%, H:2.3% and O:23.2%.Know that the condition that makes this pitch stabilization obtain stabilization material (demonstrating maximum intensity when it is made into carbon fiber) is: the heat-up rate of 1 ℃/min, 240-250 ℃ Heating temperature and about 30 minutes hold-time.Therefore, these conditions of using in this comparative example are excessive stabilization conditions, and clearly it is harsher than the best stabilized condition.
According to the mode identical with comparative example 1 with the material of this excessive stabilization 1,100 ℃ of following carbonization, obtain char-forming material with 67% productive rate based on employed intermediate phase.This char-forming material has specific surface area 13m 2/ g, (SA (BET)) records by the BET method.
Embodiment 6
Handling the fibrous powder of the high softening point bitumen that obtains by solvent extraction among the embodiment 1 mixes with the stabilization material that obtains by heating under 355 ℃ stabilization temperature in embodiment 1, obtain mixture, the content of the high softening point bitumen fiber of this mixture, promptly high softening point bitumen fiber * 100/ (stabilization material+high softening point bitumen fiber) is 0,20,30,40,60,80 and 100%, the biased sample that is obtained each has the gross weight of 10g.Each sample that mixes mixes fully, adds the dimethylbenzene of 6ml with the dissolving high softening point bitumen to them respectively then.Each mixture is mediated respectively well.By under reduced pressure from each mixture, removing removal xylene in 60 ℃ of following dryings.Then, mixture grinds in mortar respectively roughly, obtains the also tiny molded raw material of size ratio 35 orders.By using dicing machine (Okada Seiko KK, the model: N-30) with molded raw material respectively pelletizing, obtain the cylindrical molded article of diameter 3mm and length about 3mm of interior diameter as 3mm.Then, all molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Like this, molded article is stabilized.Result from embodiment 1 can be clear that, more than employed condition be by introducing the oxygen of q.s, being enough to excessively stablize the condition of high softening point bitumen.
Then, be heated to 1,000 ℃ and under this temperature, kept 1 hour and make the molded article carbonization of excessive stabilization by heat-up rate with 10 ℃/min.The outward appearance of the carbon goods that are shaped, productive rate with according to embodiment 1 in the specific surface area that records of identical method all be shown in table 7.
Result from table can recognize, the carbon goods that the material of independent use stabilization can not obtain to be shaped, when high softening point bitumen content is higher than 80%, the carbon goods that are shaped can't keep the shape of the pitch articles that is shaped, because swelling takes place because of the fusing of goods inside in the pitch articles that is shaped in carbonization process, and when the inner generation of goods was melted, having formed had the very carbon goods of a kind of shaping of low specific surface area.Can recognize, when high softening point bitumen content is 20-60%, can obtain with embodiment 1 in the same carbon goods that a kind of shaping of high specific surface area is arranged.
Table 7
Blend ratio (wt%) is the material green grass or young crops of stabilization high softening-point drop excessively Carbon goods productive rate (1)Outward appearance SA (BET) is (m (wt%) 2/g)
????100????????0 ????80?????????20 ????70?????????30 ????60?????????40 ????40?????????60 ????20?????????80 ????0??????????100 ????- (2)-39 396 39 385 40 390 37 389 46 swellings(3)12 47 swellings (3)???-
(1): based on the productive rate (2) of the carbon goods of the pitch articles of the shaping before the stabilization: can not manufacturing molded article (3): swelling when the shaping goods are stabilized
The comparative example 4
The carbon goods that attempt are shaped in accordance with the following methods: in embodiment 6 preparation, high softening point bitumen content be 20-60% shaping pitch articles according to embodiment 6 in identical mode and under identical condition, being carbonized, just do not carry out stabilization treatment.The outward appearance of the carbon goods that are shaped as, productive rate with according to embodiment 1 in the specific surface area measured by BET method (SA (BET)) of identical mode be shown in table 8
Result in this table can recognize, if save stabilization treatment for the pitch articles of employed shaping, then can only obtain the carbon goods of the shaping of low-down specific surface area.
Table 8
Blend ratio (wt%) is the material green grass or young crops of stabilization high softening-point drop excessively Carbon goods productive rate (1)Outward appearance SA (BET) is (m (wt%) 2/g)
????80????????20 ????60????????40 ????40????????60 46 0.2 43 swellings (2)0.2 39 fusings (3)??1.1
(1): based on the productive rate (2) of the carbon goods of the pitch articles of the shaping before the stabilization: to a certain degree swelling and fusion (3) are arranged when the shaping goods are carbonized: fusing and obviously being out of shape when the shaping goods are stabilized
Embodiment 7
7g is the high softening point bitumen blending in of fibers by obtaining in embodiment 2 at the stabilization material that makes of heating and 3g under 355 ℃ the stabilization temperature in embodiment 2, the dimethylbenzene of 3ml is added in this mixture dissolve high softening point bitumen then.Then, allow mixture mediate.With the same among the embodiment 6, by under reduced pressure from mixture, removing removal xylenes in 60 ℃ of following dryings.Then, mixture grinds in mortar roughly, obtains granularity less than 35 purpose shaping raw materials.Employed dicing machine obtains the cylindrical molded article of 3mm diameter and about 3mm length with this shaping raw material granulation in embodiment 6 by using.
Then, all molded article is heated to 255 ℃, 305 ℃ and 355 ℃ with the heat-up rate of 0.5 ℃/min and kept 1 hour under these temperature respectively in air atmosphere.Like this, molded article is stabilized.With the same among the embodiment 6, the molded article of stabilization is carbonized under 1,000 ℃, thereby obtains the carbon goods of shaping.
The outward appearance of the carbon goods that are shaped, productive rate and according to embodiment 1 in same mode be shown in table 9 by the specific surface area that BET method (SA (BET)) records.
Result from table 9 can recognize, if pass through the prepared stabilization molded article of stabilization treatment down 1 at 255 ℃, the words that are carbonized under 000 ℃, the specific surface area of the carbon goods that are shaped has reduced all over, when if excessively the molded article of stabilization is carbonized, the specific surface area of the carbon goods that are shaped uprises, and is suitable with the specific surface area of the fibrous carbon that obtains in embodiment 2.
At random say, for from a kind of forming carbon goods that the stabilization molded article of stabilization makes under 355 ℃ temperature, according to embodiment 1 in identical mode by Langmuir (SA (Lang)) measurement the specific area and obtain 650m 2The result of/g.
Just now the absorption that the product of mentioning records under liquid nitrogen temperature-desorb isothermal curve to be shown in Fig. 3.In Fig. 3, circle refers to the value that the value that obtains in when absorption and stain obtain when referring in desorb.Can understand from Fig. 3, the forming carbon goods can very almost adsorb all nitrogen under the relative pressure of close limit (P/Ps), have shown that promptly it is formed with the very little hole of very narrow pore size distribution.In addition, the curve with the Fig. 1 that obtains in embodiment 1 is the same basically for the absorption-desorption isothermal curve of Fig. 3.This fact means in the molded article of the material (fibrous powder) of the little shape that obtains in embodiment 1 and acquisition in the present embodiment, all forms substantially the same hole.From above data, distribute by the HK method calculated hole diameters of in embodiment 1, explaining, and find that this molded article has very narrow pore size distribution and central aperture to be measured as about 6 dusts.
Table 9
Stabilization temperature (℃) Carbon goods productive rate (1)Outward appearance SA (BET) is (m (wt%) 2/g)
????255 ????305 ????355 49 264 46 363 38 386
(1): based on the productive rate of the carbon goods of the pitch articles of the shaping before the stabilization
Embodiment 8
The high softening point bitumen blending in of fibers that 7g obtains in embodiment 2 by the stabilization fiber that makes in stabilization under 255 ℃ the temperature and 3g in embodiment 2 adds the dimethylbenzene of 3ml in this mixture then and dissolves high softening point bitumen.Then, allow mixture mediate.With the same among the embodiment 6, by under reduced pressure from mixture, removing removal xylenes in 60 ℃ of following dryings.Then, mixture grinds in mortar roughly, obtains granularity less than 35 purpose shaping raw materials.Employed dicing machine obtains the cylindrical molded article of 3mm diameter and about 3mm length with this shaping raw material granulation in embodiment 6 by using.
Then, molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Like this, molded article is stabilized.With the same among the embodiment 6, the molded article of stabilization is carbonized under 1,000 ℃, thereby obtains the carbon goods of shaping.
So the carbon goods of the shaping that obtains have good surface appearance.Productive rate based on the forming carbon goods of the high softening point bitumen goods that are shaped is 39%.These forming carbon goods are 393m by the specific surface area that BET method (SA (BET)) records it 2/ g and be 688m by the specific surface area that Langmuir method (SA (Lang)) records it 2/ g.
Just now the absorption that the product of mentioning records under liquid nitrogen temperature-desorb isothermal curve to be shown in Fig. 4.In Fig. 4, circle refers to the value that the value that obtains in when absorption and stain obtain when referring in desorb.Can understand from Fig. 4, the forming carbon goods can very almost adsorb all nitrogen under the relative pressure of close limit (P/Ps), have shown that promptly it is formed with the very little hole of very narrow pore size distribution.In addition, the curve with the Fig. 1 that obtains in embodiment 1 is the same basically for the absorption-desorption isothermal curve of Fig. 4.This fact means in the forming carbon goods that obtain in the present embodiment, has formed the micropore that extremely narrow pore size distribution is arranged.
From above data, distribute by the HK method calculated hole diameters of in embodiment 1, explaining, and find that this molded article has very narrow pore size distribution and central aperture to be measured as about 6 dusts.
Embodiment 9
Handled the high softening point bitumen fibrous powder that obtains by the solvent extraction in embodiment 1 and mix in predetermined ratio with the stabilization material that heating obtains under 355 ℃ stabilization temperature in embodiment 1, the biased sample that is obtained has the gross weight of 10g separately.Each sample mixes fully, and the dimethylbenzene that adds 6ml to them respectively dissolves high softening point bitumen then.Each mixture is all mediated respectively well.By under reduced pressure removing removal xylene in 60 ℃ of dryings.Then, mixture grinds in mortar respectively roughly, obtains granularity less than 60 purpose shaping raw materials.
Interior diameter is housed under the load of 133kg, allows shaping raw material form by using, obtain the cylindrical molded article of 6mm diameter and about 6mm length as the pressing machine of the mouth mould of 6mm.
Then, all molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Thereby molded article is stabilized.Can be clear that from the result of embodiment 1, more than employed condition be the condition that is enough to make the excessive stabilization of high softening point bitumen by the oxygen of introducing q.s.
Then, be heated to 1,000 ℃ and under this temperature, kept 1 hour and make the molded article carbonization of excessive stabilization by heat-up rate with 10 ℃/min.
Outward appearance, the productive rate of the carbon goods that are shaped and the specific surface area that is recorded by BET method (SA (BET)) are shown in table 10.
Can understand, in addition by use shaping pitch articles by the drawing method preparation can make with embodiment 6 in the same forming carbon goods with high specific surface area.
Table 10
Blend ratio (wt%) is the material green grass or young crops of stabilization high softening-point drop excessively Carbon goods productive rate (1)Outward appearance SA (BET) is (m (wt%) 2/g)
????80???????20 ????70???????30 ????60???????40 ????40???????60 39 is good (2)411 38 381 37 368 36 384
(1): based on the productive rate (2) of the carbon goods of the pitch articles of the shaping before the stabilization: well, but some embrittlement.
Embodiment 10
The high softening point bitumen blending in of fibers that 7g obtains in embodiment 2 by the stabilization material that makes in stabilization under 355 ℃ the temperature and 3g in embodiment 2 adds the dimethylbenzene of 3ml in this mixture then and dissolves high softening point bitumen.Then, allow mixture mediate.With the same among the embodiment 6, by under reduced pressure from mixture, removing removal xylenes in 60 ℃ of following dryings.Then, mixture grinds in mortar roughly, obtains granularity less than 35 purpose shaping raw materials.Employed dicing machine obtains the cylindrical molded article of 3mm diameter and about 3mm length with this shaping raw material granulation in embodiment 6 by using.
Then, molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Like this, molded article is by excessive stabilization.
In addition, by the heat-up rate with 10 ℃/min goods are heated to 400-1, the preset temperature between 300 ℃ down and kept 1 hour under these temperature and make molded article carbonization in stream of nitrogen gas of excessive stabilization.
The outward appearance of forming carbon goods, productive rate and the specific surface area that is recorded by BET method (SA (BET)) are shown in table 11.
From table, can understand, when carbonization temperature is low, promptly 400 ℃, or when too high, promptly 1,150 ℃, 1,300 ℃, specific surface area descends, and at 600 ℃, the forming carbon goods that obtain under the carbonization temperature of 800 ℃ and 1,000 ℃ have high specific surface area, with obtain among the embodiment 3 similar.
Table 11
Stabilization temperature (℃) Carbon goods productive rate (1)Outward appearance SA (BET) is (m (wt%) 2/g)
????400 ????600 ????800 ????1000 ????1150 ????1300 67 8.3 44 403 39 402 38 386 37 178 37 2.4
(1): based on the productive rate of the carbon goods of the pitch articles of the shaping before the stabilization
Embodiment 11
The micro-spherical particle of the stabilization that 6g is made by emulsion process in embodiment 5 mixes with the microspheroidal high softening point bitumen particle that 4g obtains in embodiment 5, and 4ml benzene is joined dissolving high softening point bitumen particle in the mixture.Then, mediate mixture.With the same among the embodiment 6, by under reduced pressure from mixture, removing benzene in 60 ℃ of following dryings.Then, mixture by grinding roughly, obtains granularity less than 35 purpose shaping raw materials in mortar.Employed dicing machine obtains the cylindrical molded article of 3mm diameter and about 3mm length with the shaping raw material granulation in embodiment 6 by using.
Then, molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Like this, molded article is stabilized.According to embodiment 6 in identical mode be heated to 1,000 ℃ and make the carbon goods of shaping by molded article with stabilization.
So the carbon goods that obtain have good surface appearance.Productive rate based on the forming carbon goods of the pitch articles of shaping before the stabilization is 38%.The specific surface area that is recorded by BET method (SA (BET)) of these forming carbon goods is 383m 2/ g.
Embodiment 12
7g according to the mode identical with embodiment 2 by using 355 ℃ stabilization temperature and 1, the carbon material of 000 ℃ carbonization temperature preparation mixes with the high softening point bitumen of the acquisition in embodiment 2 of 3g, the dimethylbenzene of 3ml is joined in this mixture dissolve high softening point bitumen.Then, mediate mixture.With the same among the embodiment 6, by under reduced pressure from mixture, removing removal xylenes in 60 ℃ of following dryings.Then, mixture grinds in mortar roughly, obtains granularity less than 35 purpose shaping raw materials.
By using the dicing machine that in embodiment 6, uses, obtain the cylindrical product of 3mm diameter and about 3mm length with the shaping raw material granulation.
Then, molded article is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Thus with the molded article stabilization.According to embodiment 6 in identical mode, the molded article of stabilization is heated to 1,000 ℃ and make the forming carbon goods.
So the carbon goods that obtain have good surface appearance.Productive rate based on the forming carbon goods of the pitch articles of shaping before the stabilization is 72%.It is 409m that the carbon goods that are shaped have the specific surface area that is recorded by BET method (SA (BET)) 2/ g and the specific surface area that is recorded by Langmuir method (SA (Lang)) are 848m 2/ g.From being used for measuring the adsorption isothermal curve of SA (Lang), distribute by the HK method calculated hole diameters of in embodiment 1, having explained, concurrent ready-made shape goods have very narrow pore size distribution and central aperture is measured at about 6 dusts.
The comparative example 5
By using granulation obtained in embodiment 12 cylindrical shaping pitch articles and making the forming carbon goods 1,000 ℃ of following carbonization according to the mode identical with embodiment 6.Yet, in the present embodiment, cylindrical shaping pitch articles is not carried out stabilization treatment.Productive rate based on the carbonization product of cylindrical shaping pitch articles is 72%.These carbon goods have good surface appearance, but its specific surface area that is recorded by BET method (SA (BET)) is 42m 2/ g.
Embodiment 13
14g mixes with the high softening point bitumen fiber dust that obtains in embodiment 2 of 6g by asphaltic base (pitch-based) the stabilization fiber that stabilization obtained under 255 ℃ temperature in embodiment 2,6ml dimethylbenzene is joined dissolve high softening point bitumen in the mixture then.Then, mediate mixture.According to such among the embodiment 6, under reduced pressure in 60 ℃ of dry down removal xylenes that from mixture, remove.Then, mixture grinds in mortar roughly, obtains granularity less than 20 purpose shaping raw materials.By using the dicing machine that in embodiment 6, uses, obtain the cylindrical molded article of 3mm diameter and about 3mm length with the shaping raw material granulation.
Then, molded article is heated under 255 ℃ and this temperature with the heat-up rate of 0.5 ℃/min in air atmosphere and kept 1 hour.Like this, molded article is stabilized.In addition, by in nitrogen atmosphere, being heated to 600 ℃ of predetermined temperature, 800 ℃ and 1,000 ℃ and under these temperature, keeping 1 hour respectively, make the molded article carbonization of stabilization with the heat-up rate of 10 ℃/min.
So the outward appearance of the forming carbon goods that obtain, all be shown in table 12 based on the productive rate of cylindrical shaping pitch articles and the specific surface area that records by BET method (SA (BET)).From table, can understand, when down the filler of stabilization and shaping pitch articles all are carbonized 255 ℃ (it is the condition that is not enough to obtain maximum oxygen concentration), observe high specific surface area under the carbonization temperature in 600 ℃ of-800 ℃ of scopes, but 1, under 000 ℃, specific surface area descends.So, can reach a conclusion, in order to obtain high specific surface area in wide carbonization temperature scope, for the carbonization operation, the molded article of the stabilization that preferably overuses is as raw material.
Table 12 carbonization temperature carbon goods (℃) productive rate (1)SA (BET)
(wt%) (m 2/ g) 600 62 336 800 59 336 1,000 59 77 (1): based on the productive rate of the carbon goods of the pitch articles that is shaped before the stabilization
Embodiment 14
The high softening point bitumen material of the fibrous little shape that obtains in embodiment 2 is as the starting raw material of present embodiment.Above-mentioned fibrous pitch is heated to 355 ℃ and kept 1 hour with the heat-up rate of 0.5 ℃/min under this temperature in air atmosphere.Like this, the excessive stabilization of fibrous pitch quilt.More than employed condition be enough to make the excessive stabilization of high softening point bitumen, introduce the oxygen of q.s.Productive rate based on the stabilization material of high softening point bitumen is 77%.The results of elemental analyses of stabilization material is: C:67.7%; H:2.0%; O:30.3%.
Under the atmosphere of the nitrogen of the carbonic acid gas that contains 32% (volume) and 68% (volume), be heated to 800 ℃ and under this temperature, kept 60 minutes, and make fibrous stabilization material carbonization with the heat-up rate of 10 ℃/min.
For resulting carbon products, according to embodiment 1 in identical mode, the amount of adsorbed nitrogen records specific surface area by BET method (SA (BET)) under the liquid nitrogen temperature.Similarly, according to embodiment 1 in identical mode, measure the adsorption isothermal curve of nitrogen and the specific surface area that records by Langkuir method (SA (Lang)) from this data computation then under liquid nitrogen temperature.SA (BET), SA (Lang) and be shown in table 13 based on the productive rate of the carbon products of employed stabilization material.
The result who provides from table 13 can recognize, containing when the stabilization material by method preparation of the present invention under the atmosphere of carbonic acid gas to be carbonized, and can obtain the porous carbon material that is rich in aperture of high specific surface area.
Embodiment 15-24
Be carbonized under the various conditions that the stabilization material of using in embodiment 14 provides in table 13, be that gas concentration lwevel is 21% (volume)-100% (volume), heat-up rate is 10 ℃/min, and it is 60 minutes-180 minutes with carbonization time that carbonization temperature is 800 ℃-1,000 ℃.The productive rate and the specific surface area of the carbon material that is obtained are shown in table 13.The result who provides from table 13 can recognize that the specific surface area of carbon material depends on the carbonization condition and can obtain to be rich in aperture and the very carbon material of bigger serface is arranged when carrying out carbonization under the atmosphere that is containing carbonic acid gas.
For the porous carbon material that in embodiment 16 and embodiment 24, obtains,, under liquid nitrogen temperature, recorded the adsorption isothermal curve of nitrogen respectively by using the same instrument (BELSORP) that in embodiment 1, is used for measuring adsorption isothermal curve.The adsorption isothermal curve that the adsorption isothermal curve of embodiment 16 is shown in Fig. 5 and embodiment 24 is shown in Fig. 6.From these figure, for calculate by the DH method at relative pressure (P/Ps): (this is corresponding to the aperture that is not more than 20 dusts (micropore)) below 0.09, investigate nitrogen adsorptive capacity: % (volume), i.e. (volume/cumulative volume of adsorbable nitrogen under Ps of the nitrogen of actual absorption under P) * 100 and at relative pressure (P/Ps): (corresponding to the aperture that is not more than 40 dusts) 0.44 below investigation nitrogen adsorptive capacity: % (volume).The result provides below.
P/Ps 0.09 following P/Ps 0.44 following examples 16 95vol% 99vol% embodiment 24 67vol% 95vol%
By the vol% that records the micropore of the carbon material that is obtained with above mentioned identical mode in embodiment 15 and embodiment 23 is respectively 98% (volume) and 94% (volume).Can recognize that from The above results the hole that contains in the porous carbon materials of Huo Deing has extremely narrow diameter Distribution and size uniformly in these embodiments, with usual production Comparatively speaking.
Embodiment 25 and 26.
By in nitrogen atmosphere, being heated to 800-900 ℃ and under this temperature, kept the stabilization material carbonization that will prepare 60 minutes according to mode similarly to Example 14 with the heat-up rate of 10 ℃/min.The productive rate of the material that is obtained and specific surface area also are shown in table 13.Result from table 13 can understand, and can obtain very high specific surface area when carbonization is carried out under oxidizing condition.
Table 13-a embodiment No. 14 15 16 17 18 19 20CO 2Concentration 32 32 32 100 100 100 21 (vol%) N 2Concentration (vol%) 68 68 68 000 79 carbonization temperatures (℃) productive rate 54 50 35 53 47 20 40 of 800 900 1,000 800 900 1,000 1000 carbonization times (min), 60 60 60 60 60 60 60 carbon materials (1)(wt%) SA (BET) 430 480 680 420 540 790 620
(m 2/g)??SA(Lang)????????750??890???1760??760??1160?2590?1500
(m 2/ g) (1): based on the productive rate of the carbon material of employed stabilization material
Table 13-b embodiment No. 21 22 23 24 25 26CO 2Concentration 44 32 32 32 00 (vol%) N 2Concentration (vol%) 56 68 68 68 100 100 carbonization temperatures (℃) productive rate 31 54 44 8 56 55 of 1,000 800 900 1,000 800 900 carbonization times (min), 60 180 180 180 60 60 carbon materials (1)(wt%) SA (BET) 710 440 550 850 390 390
m 2/ g) SA (Lang) 2,020 800 1,220 3,100 650 650 (m 2/ g) (1): based on the productive rate of the carbon material of employed stabilization material
Embodiment 27-30
According to embodiment 14 in identical mode prepare fibrous stabilization material, just treatment temp is 255 ℃.Productive rate based on employed high softening point bitumen is 103%.Though the best stabilized condition is used for stablizing pitch, and then obtain the productive rate of the maximum of char-forming material, the oxygen concn in stabilization material (23.5%) is still fully unsaturated.By in the atmosphere of 32vol% carbonic acid gas with the heating of the heat-up rate of 10 ℃/min and under 800-1000 ℃ temperature, kept 60-180 minute, make the material carbonization of this stabilization.The productive rate and the specific surface area of resulting char-forming material are shown in table 14.
Result in this table has shown, even stabilization material is unsaturated fully by oxygen, according to the method for these embodiment, by containing the porous carbon material that carbonization under the atmosphere of carbonic acid gas can obtain aperture and big specific surface area.
By using scanning electronic microscope, (specific surface area that is recorded by Langmuir method (SA (Lang)) is higher than 3,000m to the porous carbon material that obtains in embodiment 30 2/ g) observe the resulting Fig. 7 of the results are shown in.This porous carbon material has fiber shape, the mean diameter of 12-13 μ m of having an appointment and tens microns length.Almost (specific surface area that is recorded by the Langmuir method is 490m to the apparent volume of this material with the material that obtains with 62% productive rate in embodiment 27 2/ g) identical.Carbonization productive rate in embodiment 30 is obviously less than normal, although apparent volume is almost identical with the product with less specific surface area, this fact shows that this carbon material has at the inner evenly hole of development of fibrous carbon.
Table 14 embodiment No. 27 28 29 30 CO 2Concentration 32 32 32 32 (vol%) N 2Concentration (vol%) 68 68 68 68 carbonization temperatures (℃) productive rate 62 51 42 13 of 800 900 1,000 1000 carbonization times (min), 60 180 60 180 carbon materials (1)(wt%) SA (BET) 320 510 620 850 (m 2/ g) SA (Lang) 490 1,050 1,580 3070 (m 2/ g) (1): based on the productive rate of the material of fibrous stabilization
Embodiment 31-35
14g according to embodiment 14 in identical mode (except stabilization temperature is 255 ℃) obtain fibrous stabilization material and be used as filler.The binding agent of this filler and 6g (it be according to embodiment 14 in the fibrous powder of the high softening point bitumen that obtains of identical mode) mix.6ml dimethylbenzene is joined in this mixture, to be dissolved in the high softening point bitumen that mixture is contained.Mixture is mediated.Mixture is 60 ℃ of following vacuum-dryings, thereby removes removal xylene.Resistates grinds in mortar roughly, and the granularity of acquisition is less than the Powdered shaping raw material of 35 purposes.
By use be equipped with diameter as the mouth mould of 3mm dicing machine (model: N-30, OkadaSeiko Co. Ltd.) with this shaping raw material granulation, obtain diameter and are 3mm and the length cylindrical pellets for about 3mm.
Heat-up rate with 0.5 ℃/min heats this pellet and made pellet stable in 1 hour 355 ℃ of following maintenances.By introducing the oxygen of q.s, these conditions are enough to excessively stablize high softening point bitumen.
Then, by at gas concentration lwevel be in the atmosphere of 32vol% or 100vol% with the heat-up rate heating of 10 ℃/min and at 900-1,000 ℃ kept 30-120 minute down and makes the carbonization of stabilization shaped material.Productive rate and specific surface area based on the carbonization product of the resulting shaping of the molded article of stabilization all are shown in table 15.
The result shows in the table, uses oxidizing gas atmosphere by the method according to this invention in carbonizing treatment, can obtain big specific surface area and foraminate porous carbon material, the processing even this material is formed.The specific surface area of the molded article almost specific surface area with the material of fibrous little shape is identical, and this shows that this molded article is made up of the even carbon with the even hole that partly produces from filler and partly produce from binding agent.For porousness carbon goods, promptly according to embodiment 16 in the pellet that in embodiment 34, obtains of identical mode, measure the adsorption isothermal curve of nitrogen under liquid nitrogen temperature, calculate pore ratio.It is 84% that the pore ratio of porousness forming carbon goods is recorded.
Table 15 embodiment No. 31 32 33 34 35 CO 2Concentration 32 100 100 100 100
(vol%) N 2Concentration (vol%) 68 0000 carbonization temperatures (℃) productive rate 37 41 33 21 11 of 1,000 900 1,000 1,000 1000 carbonization times (min), 60 120 30 60 80 carbon goods (1)(wt%) SA (BET) 660 630 710 790 880 (m 2/ g) SA (Lang) 1,700 1,560 2,030 2,900 3380 (m 2/ g) (1): based on the productive rate of pellet before the stabilization
Embodiment 36 and 37
The petroleum naphtha pressure tar that 100g uses in embodiment 14 is heated to 80 ℃ and with 5, the rotating speed of 000rpm is at homogenizer (POLYTORON, trade(brand)name, by KINEMATICA company, Switzerland makes) the middle stirring, add 10g nonionogenic tenside (polyoxyethylene nonylplenyl ether, Emulgen985 simultaneously, trade(brand)name is made by Kao Corp. (KAO. Corp. SA)).After fully stirring, the ion exchanged water of 300ml is added gradually, obtain the xanchromatic emulsion, and the petroleum naphtha pressure tar is dispersed in wherein with fine particulate form.
The mixed solvent of this emulsion and SBA and MEK (volume ratio 80: 20) is equipped with in the jar of agitator by using independent pump to be added drop-wise to continuously in 1: 10 by volume, and mixes to come the light constituent in the extraction feed and remove from emulsion and anhydrate.Mixture reclaims sedimentary insoluble component through centrifugal treating, and SBA by using 10 times of volumes and the mixture of MEK extract once more then.Use methyl alcohol, repeat same operation and wash solid ingredient twice.
Resulting solid matter is in addition dry under 60 ℃ under vacuum, and obtaining a kind of softening temperature is that 242 ℃ (being measured by temperature gradient method) and median size are the spheroidal particle of the high softening point bitumen of about 3 μ m.Productive rate based on the product of raw material petroleum naphtha pressure tar is 25%.
This high softening point bitumen is heated to 360 ℃ and kept 1 hour and make the pitch stabilization with the heat-up rate of 0.5 ℃/min under this temperature, thereby obtains the material of stabilization with 68% productive rate based on initial high softening point bitumen.
The material of this stabilization is by being heated to 800-900 ℃ and keep being able in 60 minutes carbonization under this temperature with the heat-up rate of 10 ℃/min in the atmosphere of 100% (volume) carbonic acid gas.The productive rate and the specific surface area of resulting char-forming material are shown in table 16.
The result shows in the table, even when producing high softening point bitumen by emulsification method, also can obtain big specific surface area and foraminate porous carbon material by aforesaid method.
Embodiment 38
According to embodiment 36 in the spheroidal particle of the stabilization that obtains by emulsification of identical mode in nitrogen atmosphere, be heated to 1,000 ℃ and under this temperature, kept 60 minutes with the heat-up rate of 10 ℃/min.The productive rate and the specific surface area of resulting char-forming material are shown in table 16.Result in this table shows that carbonization can not make specific surface area improve the specific surface area that reaches carbonization in oxidizing gas atmosphere in inert atmosphere, even when using higher temperature.
Table 16 embodiment No. 36 37 38CO 2Concentration (vol%) 100 100 0 N 2Concentration (vol%) 00 100 carbonization temperatures (℃) productive rate 50 18 53 of 800 900 1000 carbonization times (min), 60 60 60 carbon materials
(1)(wt%) SA (BET) (m 2/ g) 470 680 420SA (Lang) (m 2/ g) 900 1,850 760 (1): based on the productive rate of stabilization spheroidal particle
Embodiment 39 and 40
The molded article of stabilization, the i.e. pellet that obtains in embodiment 31 is by in the nitrogen of 1: 1 (mol ratio) and steam (vapour concentration: be heated to 800-900 ℃ and keep being able in 1 hour carbonization under this temperature with the heat-up rate of 10 ℃/min in the atmosphere 50 moles of %).The productive rate and the specific surface area of resulting char-forming material are shown in table 17.The result shows in the table, uses steam can produce porous carbon material as the carbonizing treatment of oxidizing gas, and its specific surface area is the same big as the specific surface area that carbonizing treatment obtained of oxidizing gas with the use carbonic acid gas.
According to embodiment 16 in identical mode, measure the adsorption isothermal curve of the porous carbon material nitrogen under liquid nitrogen temperature in embodiment 40, obtained.The results are shown in Fig. 8.From this figure, for relative pressure (P/Ps): (corresponding to 20 dusts or the aperture below 20 dusts) below 0.09, it is 84% that the micropore ratio corresponding with the nitrogen adsorptive capacity recorded.
Table 17
Concentration (mol%) 50 50 N of embodiment No. 39 40 steam 2Concentration (mol%) 50 50 carbonization temperatures (℃) productive rate of 800 900 carbonization times (min), 60 60 carbon goods (1)(wt%) 40 16 SA (BET) (m 2/ g) 600 770 SA (Lang) (m 2/ g) 1,420 2680 (1): based on the productive rate of stabilization molded article
Embodiment 41-43
By being used for the ice-cooled trap of tail gas refrigerative, being linked in sequence in the outlet of carbide furnace heating tube by this as the rubber sphere and the diaphragm type gas recycle pump of tail gas reservoir, so that will be circulated to the inlet of heating tube from the outlet of circulating pump expellant gas, thereby make carbonizing plant.If in the system of this device, produce gas, can be from the expansion estimation gas volume roughly of rubber sphere.
With 7g according to embodiment 14 in the stabilization material for preparing of identical mode put into the heating tube of carbide furnace.After the atmosphere of whole exchange systems inside, be heated to by heat-up rate and kept 60-360 minute under 1,000 ℃ and this temperature and make the stabilization material carbonization with 10 ℃/min with nitrogen.In the treating processes of this system, clearly seen under 400 ℃ or higher temperature as the rubber sphere of pneumatic reservoir and to be expanded.By 800-900 ℃ of following visual inspection, confirm that the gas volume that is produced is the 1-2 liter.Suppose that oxygen all in stabilization material discharges as carbonic acid gas, according to results of elemental analyses: C:67.7%, H:2.0% and O:30.3%, the amount of carbon dioxide that discharges from the 7g sample is about 1.5 liters as calculated.This calculated amount of carbonic acid gas is roughly corresponding to the viewed amount of visual inspection.
The productive rate and the specific surface area of resulting char-forming material are shown in table 18.The result shows in the table, even by using the carbonic acid gas that produces in carbonization process to carry out carbonizing treatment, also can obtain the porous carbon material of fully big specific surface area.
Table 18 embodiment No. 41 42 43 carbonization temperatures (℃) productive rate of 1,000 1,000 1000 carbonization times (min), 60 180 360 carbon goods (1)(wt%) 52 49 45 SA (BET) (m 2/ g) 440 480 520 SA (Lang) (m 2/ g) 820 880 1090 (1): based on the productive rate of stabilization material
The comparative example 6
To gac A and the gac B that commercial sources obtains, be determined at relative pressure (P/Ps) and be the 0.09 micropore ratio corresponding when following with the nitrogen adsorptive capacity, wherein the specific surface area of this gac A and B is about 1,000-2,000m 2/ g (measured by use nitrogen adsorptive capacity by the Langmuir method) is to use adsorption isothermal curve survey meter BELSORP (model: 28SA) the adsorption isothermal curve measuring result of resulting nitrogen.This result is shown in the table 19 with the result of embodiment 16, embodiment 23 and embodiment 40.
The result shows in the table, porous carbon material by method preparation of the present invention has higher micropore ratio, so, by the porous carbon material of method of the present invention preparation than almost having the commerical prod of same specific surface area that narrower pore size distribution and more uniform hole are arranged.
Table 19 embodiment No. SA (BET) SA (Lang) micropore ratio
(m 2/ g) (m 2/ g) (vol%) gac A 510 1,160 70 gac B 680 1,850 83 in embodiment 16, obtain 680 1,760 95 in embodiment 23, obtain 550 1,220 94 in embodiment 40, obtain 770 2,680 84
Comparative example 7-9
The powder of the high softening point bitumen that in comparative example 2, obtains in air by the heat-up rate with 0.5 ℃/min be heated to 300 ℃ and under this temperature maintenance be able to stabilization in 5 hours, then in the atmosphere that does not contain carbonic acid gas or contain in the atmosphere of 100% (volume) carbonic acid gas heat-up rate with 10 ℃/min and be heated to 1,000 ℃ and under this temperature, kept 60-90 minute and be able to carbonization.Productive rate and specific surface area based on the char-forming material of stabilization material are shown in table 20.For the char-forming material that in comparative example 9, obtains, measured the ratio that is of a size of 20 dusts or the micropore below 20 dusts by the observed value that uses the nitrogen adsorption isothermal curve under the liquid nitrogen temperature and also be shown in the table.
The result shows in the table, when isotropic pitch is used as raw material, compares with the product of method preparation of the present invention, and the reaction in nitrogen or in carbonic acid gas is to be less (being the void distribution broad) with the micropore ratio slowly.
Table 20 comparative example No. 789 CO 2Concentration (vol%) 0 100 100 N 2Concentration (vol%) 100 00 carbonization temperatures (℃) productive rate (wt%) 80 59 52 SA (the BET) (m of 1,000 1,000 1000 carbonization times (min), 60 60 90 carbon materials 2/ g) 50 460 560 SA (Lang) (m 2/ g)--880 micropore ratio (vol%)--79
Comparative example 10 and 11
The powder of the high softening point bitumen that in comparative example 1, obtains in air by the heat-up rate with 0.5 ℃/min be heated to 320 ℃ and under this temperature maintenance be able to stabilization in 5 hours, then in the atmosphere that does not contain carbonic acid gas or contain in the atmosphere of 100% (volume) carbonic acid gas heat-up rate with 10 ℃/min and be heated to 1,000 ℃ and under this temperature, kept 60 minutes and be able to carbonization.Productive rate and specific surface area (being measured by the BET one point method) based on the char-forming material of stabilization material are shown in table 21.
The result shows in the table, and when this mesophase pitch was used as raw material, the reaction in nitrogen or in carbonic acid gas was very slowly and is difficult to produce micropore.
Table 21 comparative example No. 10 11CO 2Concentration (vol%) 0 100 N 2Concentration (vol%) 100 0 carbonization temperatures (℃) productive rate (wt%) 75 74 SA (the BET) (m of 1,000 1000 carbonization times (min), 60 60 carbon materials 2/ g) 20 50
Embodiment 44
The CCl of the porous carbon material that measurement prepares in embodiment 20,21,19 and 30 4Adsorptive capacity.
Sample put into thermo-balance and carry out the desorb operation, this operation is included in and is heated to 450 ℃ in the nitrogen gas stream, keeps 1 hour under this temperature and cool to room temperature then.At room temperature allow nitrogen bubble contain CCl then by one 4Bottle, make CCl 4Evaporation.This gas is introduced into the variation of measuring weight in the desorb sample in the thermo-balance.At this moment, because do not contain CCl having put into sample and introduced 4The thermo-balance of nitrogen in and do not placing sample and introducing contains CCl 4The thermo-balance of nitrogen in all do not observe changes in weight, be considered to by CCl in the increase that has sample and contain weight under the situation that the nitrogen of CCl passes through 4Absorption cause.
The weight increase is because CCl to suppose (to reach the maximum needed time for making changes in weight) in 4 hours 4Absorption, to 1g sample determination CCl 4Adsorptive capacity (g).The results are shown in table 22.
Can find out that from table 22 porous carbon material that is prepared by method of the present invention demonstrates big CCl 4Loading capacity.
Table 22 embodiment No. SA (BET) SA (Lang) CCl 4Adsorptive capacity
(m 2/ g) (m 2/ g) (g/g sample) in embodiment 20, obtain 620 1,500 0.64
In embodiment 21, obtain 710 2,020 1.06
In embodiment 19, obtain 790 2,590 1.63
In embodiment 30, obtain 850 3,070 2.12
{。##.##1},
Embodiment 45
Be heated to 300 ℃ of weight loss that in thermo-balance, record and be 59.5%, 30 ℃ of following viscosity be 1.8 pools, dimethylbenzene insolubles content be 0% and quinoline insolubles content be that 0% petroleum naphtha pressure tar distills under vacuum, obtaining softening temperature is the low softening point asphalt of 71 ℃ (being recorded by temperature gradient method).This bituminous productive rate based on the petroleum naphtha pressure tar is 52%.This bituminous dimethylbenzene insolubles content is 0%, and quinoline insolubles content is 0%, ultimate analysis value C:92.9%, and H:7.0%, S:0.02% and H/C atomic ratio are 0.90.The dimethylbenzene of 50 weight parts mixes with this low softening point asphalt of 50 weight parts, is the solution of 0.19 pool 30 ℃ of following viscosity to dissolve this pitch and to produce a kind of.
By using the solution-air two-fluid spray nozzle (model: AM12S-IS that immerses about 3cm degree of depth, by Atomax Co., Ltd. make) this bituminous solution is ejected in 3 liters of 1000ml sec-butyl alcohols (SBA) in the glass flask, the nitrogen injection speed is 15,21 or 25l/min.When reaching about stopping 7% time, the amount at SBA medium pitch solution sprays.The whole slurry that is obtained is 2, centrifugal treating under the 000rpm, make liquid and solids constituent from.After in solid, adding the fresh SBA of 500ml, stir the mixture and the recentrifuge processing, remove soluble substance.The methanol mixed of resulting solid and 500ml and by centrifugal treating make liquid and solids constituent from.This lock out operation repeats 3 times.The final solid matter that obtains obtained the fine particle of high softening point bitumen in 3 hours 60 ℃ of following vacuum-dryings.Based on this bituminous productive rate as the low softening point asphalt of starting raw material, softening temperature and mean particle size are shown in table 23.
Can find out that can obtain softening temperature by aforesaid method is 180 ℃ or higher high softening point bitumen from table, in addition, when the flow velocity of jet flow stream improved, mean particle size descended, although as broad as long on productive rate and softening temperature.That is, can control the size of microparticle by the flow velocity of regulating jet flow stream.The shaped particles that is obtained when the flow velocity of jet flow stream is 25l/min is observed by using scanning electronic microscope.Photo is given in Figure 10.The particle of the little shape that is obtained by this method is irregular, and this product is the mixture of flaky material (aggregate that is considered to thin rod, aggregated particles, rod-shpaed particle etc.).
The flow velocity of table 23 jet flow stream (l/min) 15 21 25 productive rates (wt%) 53 54 52 softening temperatures (℃) 199 201 202 mean particle sizes (μ m) 8.3 5.5 4.8
Embodiment 46
Four cone-shaped stainless steel covers that have nothing in common with each other are provided, and each distance that jet space is arranged is 65-200mm and the perforate of attached opening diameter in the 100-200mm scope is arranged.Solution-air two-fluid spray nozzle (model: AM12S-IS, by Atomax Co., Ltd. makes) is fixed to the top of each cone-shaped stainless steel cover, is used for regulating the frame (jig) of jet space with structure.Frame is put into the jar of being made by stainless steel, and the volume of each jar is 9 liters and the SBA of 1000ml is housed.Each frame is installed in the jar and requires to make the attaching hole of frame to immerse about 10mm among the SBA.The distance of jet space (it is the distance from nozzle to the SBA fluid surface) is respectively 65,130,180 and 200mm.The profile of this device is shown among Fig. 9.In the accompanying drawings, numeral 1 is meant the pipeline that is used to provide raw material, numeral 2 is meant the pipeline that is used to provide jet flow stream, numeral 3 is meant two-fluid formula nozzle, numeral 4 is meant the frame of the distance (being the distance of jet space) between the surface that is used for being adjusted in nozzle and employed organic solvent, numeral 5 is meant the container that is used for storing organic solvent, and numeral 6 is meant the surface of organic solvent and numeral 7 is meant the small droplet that sprays from nozzle path.
By using this device, nitrogen sprays from nozzle with the flow velocity of 25l/min (nitrogen) and 240l/min (bituminous solution) respectively with the bituminous solution that makes by the mode identical with embodiment 45.When the amount at SBA medium pitch solution reaches about 15% the time, stop to spray.All the slurry from bituminous solution and SBA acquisition of amount filters by the G-4 glass filter.Use methanol wash resistates (being retained in the solid matter on the strainer) then, and under vacuum the dry microparticle that obtains high softening point bitumen.Based on the productive rate of the microparticle of low softening point asphalt, softening temperature and coating of particles are shown in Table 24.In Figure 11, provided the distance that takes by scanning electronic microscope and be the photo of the microparticle that obtains under the 130mm in jet space.Can find out from the result, as long as consider employed in the present embodiment raw material, device and condition, although the productive rate of microparticle almost is the same with softening temperature with the range-independence of jet space,, particle becomes sphere when the distance of jet space surpasses 130mm.
Table 24 jet space apart from productive rate softening temperature coating of particles, (mm), (wt%), (℃) 65 51 191 uncertain 105 50 194 uncertain 130 52 193 spherical 145 51 192 spherical 165 50 191 spherical 200 51 195 spheries

Claims (24)

1, a kind of preparation has the method for the porous carbon materials that is rich in aperture of high-specific surface area, and this method comprises:
(starting raw material)
Use starting raw material, it is a H/C atomic ratio heavy oil in the 0.8-1.2 scope and that be substantially devoid of the component that is insoluble to the BTX solvent, or use the low softening point asphalt that obtains from heavy oil by from described heavy oil, removing light constituent, this low softening point asphalt to have the softening temperature (measuring) below 150 ℃ or 150 ℃ and be substantially devoid of the component that is insoluble to the BTX solvent by temperature gradient method;
(the first step)
Form the material of the little shape that is of a size of 100 μ m or particle, powder or fiber shape below the 100 μ m from starting raw material;
(second step)
By allowing the material of little shape contact and from the material of little shape, extract light constituent with organic solvent, this solvent can cause that the material of little shape of 10wt% keeps as insoluble component at least, thus obtain softening temperature be (measure) more than 180 ℃ or 180 ℃ by temperature gradient method, be the high softening point bitumen material of 5wt% or a kind of little shape below the 5wt% and that be substantially devoid of the component that is insoluble to the BTX solvent through being heated to 300 ℃ of shown weight loss that go out;
(the 3rd step)
High softening point bitumen by the little shape of heating in oxygen-containing atmosphere makes it stable, thereby obtains the material of stabilization; With
With the carbonization in statu quo of resulting stabilization material, or will be by mixing, be shaped as the stabilization material of filler and binder pitch (it be according to the method preparation the same with the high softening point bitumen material of little shape of in second step, mentioning) and making resulting molded article stabilization and the asphaltic base stabilization molded article carbonization that makes.
2, according to the desired method of claim 1, the porous carbon materials that wherein is rich in aperture has by the BET method and is 300m by the specific surface area of using the nitrogen adsorptive capacity and recording 2/ g or 300m 2More than/the g.
3, according to the desired method of claim 1, wherein in the 3rd step, be used for making the condition of high softening point bitumen material settling outization of little shape harsher than the best stabilized condition, carbonization temperature is at 400-1, in 100 ℃ of scopes.
4,, wherein in the 3rd step, be used for making the condition of the high softening point bitumen material settling outization of little shape to be enough to obtain the material of little shape of a kind of stabilization that wherein oxygen concn is saturated basically according to the desired method of claim 3.
5, according to any one desired method among the claim 1-4, wherein carbonization be in inert atmosphere at 500-1, carry out under the temperature in 100 ℃ of scopes.
6, according to the method for claim 5, the wherein said porous carbon materials that is rich in aperture has by the BET method and is 300m by the specific surface area of using the nitrogen adsorptive capacity to be measured 2/ g or 300m 2More than/the g and central aperture less than 10 dusts.
7, according to any one desired method among the claim 1-4, wherein carbonization be in oxidizing gas atmosphere at 400-1, carry out in 000 ℃ the temperature range.
8, according to the method for claim 7, the porous carbon materials that wherein is rich in aperture has by the BET method and is 400m by the specific surface area of using the nitrogen adsorptive capacity to be measured 2/ g or 400m 2More than/the g and central aperture less than 40 dusts.
9, according to any one desired method among the claim 1-8, wherein the stabilization material that obtains in the 3rd step is by the former state carbonization.
10, according to any one desired method among the claim 1-8, wherein the stabilization material that obtains in the 3rd step is made into molded article by using binder pitch, and wherein this binder pitch is the high softening point bitumen that makes according to the mode identical with high softening point bitumen; With the molded article stabilization; With molded article carbonization with resulting asphaltic base stabilization.
11, according to the method for claim 10, the method that wherein is used for preparing the molded article of asphaltic base stabilization comprises:
(the 4th step)
Allow as the stabilization material of filler with as the high softening point bitumen of binder pitch (it be according to the method preparation the same) with the high softening point bitumen material of in second step, mentioning, according to making that the amount of high softening point bitumen is that a kind of like this ratio of the 20-70wt% of amount of the mixture is mixed, mixture is pulverized on arbitrariness ground, thereby obtains the raw material for shaping usefulness;
(the 5th step)
To be shaped is shaped with raw material, obtains molded article, is 5mm or below the 5mm from the center to the shortest distance of outside surface wherein; With
(the 6th step)
The heating molded article makes filler part and binding agent partially stabilized simultaneously in oxygen-containing atmosphere.
12, according to any one desired method among the claim 1-11, wherein heavy oil is the pressure fuel in oil source, and it is selected from the heavy oil that obtains with by-product form and when hydro carbons heavy oil with the by-product form acquisition during by the fluid catalytic cracking process cracking when making alkene by the thermally splitting of petroleum naphtha or gasol.
13, according to any one desired method among the claim 1-12, wherein starting raw material is made into the material of little shape by pulverizing, melt-spinning, emulsification or injection.
14, according to any one desired method among the claim 1-12, the method that wherein is used for making the material of little shape in the first step is undertaken by using two-fluid spray nozzle type jet apparatus or multiple arrangement.
15, according to any one desired method among the claim 1-14, wherein the organic solvent that uses in second step is selected from the paraffinic of 5-8 carbon atom, the alcohols that 1-6 carbon atom arranged has the ketone of 3-6 carbon atom and two or more the mixture in these solvents.
16, according to any one desired method among the claim 1-12, wherein starting raw material is made into the material of little shape by emulsification and the organic solvent that uses is selected from the alcohols of 1-6 carbon atom in second step in the first step, the ketone that 3-6 carbon atom arranged, and two or more mixture in these solvents.
17, a kind of porousness pitch base carbon material, it is rich in aperture and has by the BET method and is 300m by using the measured high-specific surface area of nitrogen adsorptive capacity 2/ g or 300m 2More than/the g, this porous carbon material is by following acquisition: the bituminous material that forms little shape of particle, powder or fiber shape from the heavy oil of H/C atomic ratio in the 0.8-1.2 scope; Use the bituminous material of organic solvent extraction this little shape of taking for apple remove light constituent with obtain softening temperature by temperature gradient method mensuration be more than 180 ℃ or 180 ℃, through be heated to 300 ℃ of shown weight loss that go out as 5wt% or below the 5wt%, be substantially devoid of the component that is insoluble to the BTX solvent with a kind of high softening point bitumen material of H/C atomic ratio in the 0.8-1.2 scope; Make the high softening point bitumen stabilization; And with the material carbonization of asphaltic base stabilization.
18, according to the porous carbon material of claim 17, porous carbon material is by in inert atmosphere the material carbonization of asphaltic base stabilization being obtained, and has central aperture and be lower than 10 dusts.
19, according to the porous carbon material of claim 17, wherein porous carbon material is by in oxidizing gas atmosphere the material carbonization of asphaltic base stabilization being obtained, and to have the specific surface area of being measured by the BET method be 400m 2/ g or 400m 2More than/the g and central aperture less than 40 dusts.
20, according to the porous carbon material of claim 17, wherein porous carbon material is the forming carbon goods by following method preparation: allow as the material of the asphaltic base stabilization of filler and as a kind of softening temperature of measuring by temperature gradient method of binding agent be more than 180 ℃ or 180 ℃, through be heated to 300 ℃ of shown weight loss that go out be 5wt% or below the 5wt%, be substantially devoid of the component and the high softening point bitumen of H/C atomic ratio in the 0.8-1.2 scope that are insoluble to the BTX solvent and form together; Make the molded article stabilization; With molded article carbonization with stabilization.
21, according to the forming carbon goods of claim 20, wherein the forming carbon goods are by in inert gas atmosphere the carbon goods carbonization of stabilization being obtained, and its central aperture is less than 10 dusts.
22, according to the forming carbon goods of claim 20, wherein the forming carbon goods are by in oxidizing gas atmosphere the molded article carbonization of stabilization being obtained, and to have the specific surface area of being measured by the BET method be 400m 2/ g or 400m 2More than/the g and central aperture less than 40 dusts.
23, a kind of material of asphaltic base stabilization, it is by following preparation: the bituminous material that forms little shape of particle, powder or fiber shape from the heavy oil of H/C atomic ratio in the 0.8-1.2 scope; Use for the bituminous material of organic solvent extraction this little shape of extraction usefulness remove light constituent with obtain softening temperature by temperature gradient method mensuration be more than 180 ℃ or 180 ℃, through be heated to 300 ℃ of shown weight loss that go out as 5wt% or below the 5wt%, be substantially devoid of the component that is insoluble to the BTX solvent with a kind of high softening point bitumen of H/C atomic ratio in the 0.8-1.2 scope; With make the high softening point bitumen stabilization.
24, according to the material of the asphaltic base stabilization of claim 23, wherein the material of this asphaltic base stabilization is the molded article by the asphaltic base stabilization of following method preparation: from as the material of the stabilization of filler and as a kind of softening temperature of measuring by temperature gradient method of binding agent be more than 180 ℃ or 180 ℃, through be heated to 300 ℃ of shown weight loss that go out be 5wt% or below the 5wt%, be substantially devoid of the component and the high softening point bitumen of H/C atomic ratio in the 0.8-1.2 scope that are insoluble to the BTX solvent and make molded article; Make the molded article stabilization.
CN96121741A 1995-11-24 1996-11-22 Porous carbon material containing minute pores, and process for preparing the same Expired - Fee Related CN1069603C (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP7329935A JPH09143476A (en) 1995-11-24 1995-11-24 Production of porous carbon material having uniform micropore
JP329935/95 1995-11-24
JP329935/1995 1995-11-24
JP18327/96 1996-01-09
JP8018327A JPH09188565A (en) 1996-01-09 1996-01-09 Porous carbon formed body having uniform fine pore and production of the same
JP18327/1996 1996-01-09
JP8090032A JPH09255320A (en) 1996-03-19 1996-03-19 Production of porous carbon material having fine pore
JP90032/1996 1996-03-19
JP90032/96 1996-03-19

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN100526260C (en) * 2000-07-20 2009-08-12 卡伯特公司 Carbon foams and methods for making same
CN108919585A (en) * 2018-06-29 2018-11-30 东华大学 A kind of grading-hole NiO/C electrochromic display device and its preparation and application
CN109610047A (en) * 2018-12-18 2019-04-12 武汉科技大学 A method of accelerating Mesophase Pitch Fiberss oxidative stabilization
CN111180726A (en) * 2020-02-17 2020-05-19 中钢集团鞍山热能研究院有限公司 Production process and device for co-producing isotropic coke by using negative electrode material
CN111864203A (en) * 2019-04-28 2020-10-30 中国科学院上海硅酸盐研究所 High-capacitance lithium-carbon negative electrode material and preparation method and application thereof

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CN100526260C (en) * 2000-07-20 2009-08-12 卡伯特公司 Carbon foams and methods for making same
CN108919585A (en) * 2018-06-29 2018-11-30 东华大学 A kind of grading-hole NiO/C electrochromic display device and its preparation and application
CN108919585B (en) * 2018-06-29 2021-08-10 东华大学 Hierarchical pore NiO/C electrochromic display device and preparation and application thereof
CN109610047A (en) * 2018-12-18 2019-04-12 武汉科技大学 A method of accelerating Mesophase Pitch Fiberss oxidative stabilization
CN111864203A (en) * 2019-04-28 2020-10-30 中国科学院上海硅酸盐研究所 High-capacitance lithium-carbon negative electrode material and preparation method and application thereof
CN111864203B (en) * 2019-04-28 2022-01-04 中国科学院上海硅酸盐研究所 High-capacitance lithium-carbon negative electrode material and preparation method and application thereof
CN111180726A (en) * 2020-02-17 2020-05-19 中钢集团鞍山热能研究院有限公司 Production process and device for co-producing isotropic coke by using negative electrode material
CN111180726B (en) * 2020-02-17 2024-02-06 中钢集团鞍山热能研究院有限公司 Production process and device for co-producing isotropic coke by using anode material

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