CN102803136A - Method For Producing Carbon Materials - Google Patents
Method For Producing Carbon Materials Download PDFInfo
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- CN102803136A CN102803136A CN2010800275292A CN201080027529A CN102803136A CN 102803136 A CN102803136 A CN 102803136A CN 2010800275292 A CN2010800275292 A CN 2010800275292A CN 201080027529 A CN201080027529 A CN 201080027529A CN 102803136 A CN102803136 A CN 102803136A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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Abstract
Provided is an accurate method for producing a carbon material in which a high purity carbon material having an extremely low concentration of ash can be economically obtained. The method for producing a carbon material that can be used as a nonferrous metal reducing agent, a structural-use carbon material, an electric material-use carbon material, or as a raw material in each, involves an ashless coal producing process for producing ashless coal, which is modified coal, by modifying coal with the use of a solvent, an ashless coal heating process for heating the ashless coal that was produced by the ashless coal producing process, and a carbonizing process for obtaining the carbon material by carbonizing the ashless coal that was heated by the ashless coal heating process. The ratio of the number of hydrogen atoms and carbon atoms (H/C) in the ashless coal that was heated by the ashless coal heating process is in the range of 0.6 to 0.67.
Description
Technical field
The present invention relates to constitute non-ferrous metal reductive agent, structure with raw material of wood-charcoal material or electric material method of manufacture, the method for manufacture of the raw material of wood-charcoal material that particularly uses with the anodic framework material as the electrolysis of aluminum manufacturing with the raw material of wood-charcoal material of raw material of wood-charcoal material.
Background technology
Use the anodic main raw material as the electrolysis of aluminum manufacturing, use the petroleum coke of making by the residue of petroleum refinement operation usually.But because transport fuels such as petroleum coke and gasoline while output, therefore, exist: problem that feed rate is restricted and the impurity such as sulphur that in crude oil, comprise sometimes produce dysgenic problem etc. to aluminium purity.
On the other hand, the coal coke that in blast furnace legal system iron, uses has and the proximate character of petroleum coke as charcoal, occurs on market with sufficient amount with the anodic main raw material as the electrolysis of aluminum manufacturing.But therefore coal coke, has problems aspect quality owing to contain from the about 10 quality % of pit ash, thereby, can not be used for this purposes.
In addition, from the viewpoint of the raw material of low-ash raw material of wood-charcoal material, can enumerate: so-called ashless coal (super coal) (for example, with reference to patent documentation 1), recently, exploitation is carried out actively.At this, ashless coal promptly, extracts processing with coal with solvent through the following steps manufacturing, only separates dissolved composition in this solvent, afterwards, removes and desolvates.On the structure, the molecular weight of this ashless coal is that 2,3 lower molecular weight constituent extensively distributes to about 5,6 high molecular weight components from condensing aromatic nucleus.In addition, because ash content does not dissolve in solvent, therefore, ashless coal does not contain ash content in fact, under heating, demonstrates high workability, and thermal fluidity is good.In coal, also have as caking coal and under about 400 ℃, demonstrate thermoplastic material, and though ashless coal usually feed coal grade how, 200～300 ℃ of equal fusions (having softening meltbility) down.Therefore, effectively bring into play this characteristic, carry out, in addition, in recent years, attempt through using this ashless coal to make the raw material of wood-charcoal material as raw material of wood-charcoal material raw material as the application and development of coke manufacturing with tackiness agent.
Patent documentation 1: the spy of Japan opens the 2001-26791 communique
Summary of the invention
But, in the method for manufacture of in the past raw material of wood-charcoal material, have problem as follows.
Can know that as stated ashless coal does not contain ash content, have the advantage of softening meltbility, therefore, the cohesiveness material for repairing when making iron with coke as manufacturing is effective.In addition, not containing ash content is with the preferred character of anodic framework material (main raw material) as the electrolysis of aluminum manufacturing.But; When forming the carbonization (carbonization) of raw material of wood-charcoal material in that ashless coal is carried out heat treated; Ashless coal is because other general aspects foams, and this makes with anodic main raw material coke (raw material of wood-charcoal material) (the following anode that suitably is called is used coke) in the electrolysis of aluminum manufacturing becomes problem.That is, when the ashless coal of the state after just making is carried out carbonization, the low molecular compound gas (water vapour, CO, the CO that generate during by carbonization
2, hydrocarbon etc.) pore that produces is directly remaining, therefore, have and can not generate as the problem of anode with the suitable dense coke of coke.Need to prove, ashless coal is used for non-ferrous metal reductive agent or structure during with raw material of wood-charcoal material etc., also produces same problem with the electric material beyond the coke with raw material of wood-charcoal material, anode.
The present invention puts in view of the above problems and carries out, and its purpose is, the method for manufacture of raw material of wood-charcoal material that can obtain densification economically and have the highly purified raw material of wood-charcoal material of extremely low ash content concentration is provided.
The inventor studies; The result finds; For as with anode with the non-ferrous metal reductive agent headed by the coke or structure with raw material of wood-charcoal material, anode with the raw material of coke electric material in addition with raw material of wood-charcoal material etc.; Preferably the atomicity of the hydrogen of ashless coal and carbon is adjusted in the specialized range than (below, suitably be called H/C atomicity than).
For the H/C atomicity ratio with ashless coal is adjusted in the specialized range, particularly, ashless coal is carried out heat treated.Through heat treated, the removing etc. of decomposition, low molecular weight compositions of carrying out decomposition, aromatic series reaction, the oxygen-containing functional group of alkyl makes the hydrogen containing ratio reduce the variation of such chemical/physical, and the H/C atomicity is than slowly reducing.Thus, can suppress the swelling property of ashless coal, the inventor finds as a result, the foaming in the time of can suppressing carbonization, thus accomplished the present invention.
Promptly; Non-ferrous metal reductive agent of the present invention, structure with raw material of wood-charcoal material, electric material with raw material of wood-charcoal material, or the method for manufacture of the raw material of wood-charcoal material that uses as their raw material; It is characterized in that, comprising: ashless coal manufacturing process, wherein; Use solvent that coal is carried out modification, make ashless coal thus as the modification coal; The ashless coal heating process is carried out heat treated to the above-mentioned ashless coal of making in the above-mentioned ashless coal manufacturing process; And carbonation process; Obtain the raw material of wood-charcoal material through the above-mentioned ashless coal after the heat treated in the above-mentioned ashless coal heating process is carried out carbonizing treatment, the hydrogen of the above-mentioned ashless coal in the above-mentioned ashless coal heating process after the heat treated is 0.6～0.67 with the atomicity of carbon than (H/C).
According to such method of manufacture, coal is modified in ashless coal manufacturing process, thus, makes the ashless coal as the extremely low modification coal of ash content concentration.Then, in the ashless coal heating process, through this ashless coal of heat treated, the H/C atomicity of ashless coal is than being defined in 0.6～0.67 the scope.Then, in carbonation process,, obtain the raw material of wood-charcoal material through this ashless coal of carbonizing treatment.In addition, the H/C atomicity ratio of the ashless coal after the heat treated is more than 0.6, thus; Ashless agglutinating value of coal becomes fully, in addition, is below 0.67 through H/C atomicity ratio; The swelling property that suppresses ashless coal; When carbonizing treatment, suppress the foaming of ashless coal, obtain the extremely low raw material of wood-charcoal material of densification and ash content concentration.
In addition, in the method for manufacture of raw material of wood-charcoal material of the present invention, in above-mentioned ashless coal heating process, the heat treated of above-mentioned ashless coal, preferably with above-mentioned ashless coal manufacturing process in be used for above-mentioned coal modification solvent phase with solvent in the presence of carry out.
According to such method of manufacture, through using solvent, heat transfer efficiency improves, ashless coal to add thermal change even.In addition, owing to use and the solvent phase that in the modification of coal, uses solvent together, therefore, economy improves.
According to the method for manufacture of raw material of wood-charcoal material of the present invention, the raw material of wood-charcoal material that can access densification and have extremely low ash content concentration.In addition, can obtain such raw material of wood-charcoal material economically.
Description of drawings
Fig. 1 is figure in expression embodiments of the invention and the comparative example, intensity and the relation of H/C atomicity ratio.
Embodiment
Then, the method for manufacture for raw material of wood-charcoal material of the present invention at length describes.
The method of manufacture of raw material of wood-charcoal material of the present invention comprises: ashless coal manufacturing process, ashless coal heating process and carbonation process.Below, each operation is described.
< ashless coal manufacturing process >
Ashless coal manufacturing process makes the operation as the ashless coal of modification coal through using solvent that coal is carried out modification.
Need to prove that the ashless coal among the present invention is so-called super coal, remove to deash and become to assign to make with the coal of non-solubility through coal being carried out solvent extraction.This ashless coal has few ash content (ash content concentration 1.0 quality % below) and the moisture below the 0.5 quality % roughly.
As the method that obtains ashless coal, can utilize known method, solvent species is suitably to select in view of the proterties of coal with as the design of the raw material of raw material of wood-charcoal material with creating conditions.As typical method, has following method: will have big solvent solvent for coal, in most cases the mixture for aromatic solvent (solvent of hydrogen supply or non-hydrogen supply) and coal heats, and extracts the organic composition in the coal.But,, for example, preferably make ashless coal through following method for high-level efficiency more and obtain ashless coal at an easy rate.In this method, at first, heat, be extracted in soluble coal composition in the non-hydrogen supply dissolvent through mixture (slurry) with coal and non-hydrogen supply dissolvent.Then, the slurry after extracting is partly left with liquid portion and on-liquid, simultaneously, above-mentioned non-hydrogen supply dissolvent is partly left from aforesaid liquid, thus, make ashless coal.
As the coal of the raw material of ashless coal (below, be also referred to as feed coal), preferably use low grade coal.Through using cheap low grade coal, can make ashless coal more at an easy rate, therefore, can realize the further raising of economy.But employed coal is not limited to low grade coal, also can use bituminous coal as required.
Need to prove,, have: non-little caking coal, common coal, grizzle coals such as (brown coal, sub-bituminous coals etc.) as low grade coal at this.As grizzle, for example have: brown coal, brown coal moulded coal, sub-bituminous coal etc.In addition, for example, as brown coal, have: Victoria's coal, North Dakota coal, Berga coal etc. as sub-bituminous coal, have: Xi Aier bancor coal, Bi Nangan (Binungan) coal, high (the サ マ ラ Application ガ ウ) coal in Sa fiber crops hurdle etc.Grizzle is not limited to above-mentioned illustrative coal.Contain large quantity of moisture and expect that the coal that dewaters includes in the said in the present invention grizzle.Need to prove, preferably coal is ground into as far as possible little particle in advance, below the preferable particle size 1mm.
Non-hydrogen supply dissolvent is to be the coal derivative of master's solvent after mainly making with extra care from the coal carbonization resultant, with two cyclic aromatic series.Also stable when this non-hydrogen supply dissolvent is in heated condition, with the excellent affinity of coal.Therefore, under the situation of using non-hydrogen supply dissolvent, the ratio of the solvable composition that in solvent, extracts (is the coal composition at this) (below, be also referred to as extraction yield) improve, in addition, can easily reclaim solvent through methods such as distillations.As the staple of non-hydrogen supply dissolvent, can enumerate: as the naphthalene of two cyclic aromatic series, methylnaphthalene, dimethylnaphthalene, trimethyl-naphthalene etc.In addition, also comprise naphthalene class, anthracene class, fluorenes class in the composition of non-hydrogen supply dissolvent, in addition, wherein also comprise biphenyl or have the korenyl of long-chain fat family side chain with aliphatic lateral chain.
Through using non-hydrogen supply dissolvent to carry out heating and extracting, can improve the extraction yield of coal.In addition, non-hydrogen supply dissolvent is different with polar solvent, can easily reclaim, and therefore, recycles easily.In addition, need not to use hydrogen at high price and catalyzer etc., therefore, can coal can be dissolved, thus, obtain ashless coal, realize the raising of economy with less cost.
Coal concentration in solvent according to the kind of feed coal and different, is preferably the scope of 10～50 quality %, the more preferably scope of 20～35 quality % in the moisture-free coal benchmark.When the coal concentration in solvent was lower than 10 quality %, with respect to the amount of solvent, the coal components in proportions of in solvent, extracting reduces, and was therefore, uneconomical.On the other hand, coal concentration is high more preferred more.But when coal concentration surpassed 50 quality %, the viscosity of the slurry of preparation improved, and therefore, mobile, the liquid portion of slurry become difficulty easily with separate (afterwards the stating) of on-liquid part.
The Heating temperature of slurry is preferably in 300～450 ℃ scope.Heating temperature is in this scope the time, and the intermolecular combination that constitutes coal causes the demulcent thermolysis lentamente, and extraction yield is the highest.When Heating temperature was lower than 300 ℃, for weakening the intermolecular combination that constitutes coal, it was insufficient to become easily, and extraction yield is difficult to improve.On the other hand, when Heating temperature surpassed 450 ℃, it is very active that the pyrolysis of coal becomes, and causes the combination again of the thermolysis radical that is generated, and therefore, extraction yield is difficult to improve, and is difficult to cause the rotten of coal.Need to prove that Heating temperature is preferably 300～400 ℃.
The standard of heat-up time (extraction time) is for until the time that reaches dissolution equilibrium, but that it is implemented in is unfavorable economically.Therefore, according to conditions such as the particle diameter of coal, solvent types and difference cannot treat different things as the same, but be generally about 10～60 minutes heat-up time.When being lower than 10 minutes heat-up time, it is insufficient that the extraction of coal composition becomes easily.On the other hand,, can not carry out its above extraction even surpass 60 minutes heat-up time yet, therefore, uneconomical.
The extraction of soluble coal composition in non-hydrogen supply dissolvent is preferably carried out in the presence of rare gas element.This be because, when contact with oxygen, might be on fire, therefore dangerous, in addition, when using hydrogen, the cost raising.
As employed rare gas element, preferred cheap nitrogen, but do not have special qualification.In addition, temperature and the vapour pressure of employed solvent of pressure when extracting decided, and is preferably 1.0～2.0MPa.Under the situation that the steam of pressure ratio solvent forces down, solvent evaporates is not limited in can not extracting in the liquid phase.For with solvent limitation in liquid phase, need be than the vapour pressure of solvent higher pressure.On the other hand, during hypertonia, the cost of equipment, operating cost improve, and be uneconomical.
After extracting the coal composition like this, slurry is separated into liquid portion and on-liquid part.
At this, liquid portion is included in the solution of the coal composition that extracts in the solvent, and on-liquid partly is included in the solute of insoluble coal composition (coal that comprises ash content, i.e. culm) in the solvent.
As the method that pulp separated is become liquid portion and on-liquid part, usually known have: various filter methods or utilize the method for spinning.But, utilize in the filtering method, need the frequent change of strainer.In addition, utilize in the method for spinning, cause easily, therefore, in industry, be difficult to carry out these methods by not dissolving the obturation that the coal composition produces.Therefore, preferred use can be carried out the fluidic operate continuously, method falls in gravity Shen of being suitable for a large amount of processing with low cost.Thus, obtain as the liquid portion that is included in the solution of the coal composition that extracts the solvent (below, be also referred to as supernatant) from the top of gravity sedimentation tank.In addition, obtain as the on-liquid part that is included in the solute of insoluble coal composition the solvent (below, be also referred to as the solids component liquid concentrator) from the bottom of gravity sedimentation tank.
In addition, through from this liquid portion, separating non-hydrogen supply dissolvent, obtain ashless coal.
As the method for from supernatant (liquid portion), separating solvent, can use general distillation method or method of evaporation (spray-drying process etc.) etc.From supernatant, obtain not containing in fact the ashless coal of ash content.The ash oontent of this ashless coal is below the 1.0 quality %, contains ash content hardly.In addition, the moisture of this ashless coal is about below the 0.5 quality %, in addition, demonstrates the thermal value higher than feed coal.Therefore, through this ashless coal is carried out carbonization, can access the extremely low highly purified raw material of wood-charcoal material of ash content concentration.
< ashless coal heating process >
The ashless coal heating process is the operation of the ashless coal of making in the above-mentioned ashless coal manufacturing process being carried out heat treated.
Under the state of ashless coal after just making, swelling property is violent usually.Therefore, for repression of swelling, carry out heat treated.Heat treated need reach the mode of 0.6～0.67 scope with the atomicity of the hydrogen of the ashless coal after the heat treated and carbon and carry out than (H/C).
At this, do not carry out any processing, the just H/C atomicity ratio of the ashless coal of the state after making, according to the raw material coal with creating conditions of ashless coal and different, in about 0.7～1.0 scope.But, when this ashless coal is implemented heat treated, carry out decomposition, aromatic series reaction, the oxygen-containing functional group of alkyl decomposition, low molecular weight compositions the variation that the hydrogen containing ratio reduces such chemical/physical such as remove, the H/C atomicity is than slowly reducing.In addition, through heat treated, regulate making the H/C atomicity than the scope that reaches 0.6～0.67.
The H/C atomicity representes that than less than 0.6 heat treated is superfluous.When heat treated was superfluous, it is insufficient that coking property becomes, even with this ashless coal carbonization, also only can access powdered raw material of wood-charcoal material.Therefore, H/C atomicity ratio is lower than at 0.6 o'clock, can't obtain as the raw material of wood-charcoal material of anode with the raw material use of coke.On the other hand, the H/C atomicity representes that than greater than 0.67 heat treated is insufficient, in ashless coal, comprises many hydrogen.Therefore, the H/C atomicity is than surpassing at 0.67 o'clock, and ashless coal produces foaming during carbonization in the carbonation process.Like this, through the heat treated of ashless coal, with the H/C atomicity than being adjusted in 0.6～0.67 the scope, thus, in the coking property of remaining appropriateness, the foaming in the time of can suppressing ashless coal carbonizing.
The methods of heating treatment of ashless coal does not have special qualification, can carry out through known method.For example, in vacuum, high pressure, inert atmosphere, ashless coal is heated to 350～500 ℃, preferably is heated to 380～460 ℃.The needed treatment time is according to the proterties of ashless coal, treatment temp and difference, roughly 10 minutes to 5 hours scope.Like this, come suitably to regulate treatment temp, treatment time through the proterties of considering ashless coal, with the H/C atomicity than being controlled in 0.6～0.67 the scope.
In addition, the heat treated of ashless coal, preferably with ashless coal manufacturing process in be used for coal modification solvent phase with solvent in the presence of carry out.
That is, ashless coal carries out heat treated after with the mode that forms pulp-like and solvent.Solvent phase does not have special qualification for the amount of ashless coal, and from the viewpoint of slurry of the viscosity that obtains appropriateness, the ashless coal concentration in solvent is for example counted 10～50 quality % with the moisture-free coal benchmark, and the scope that is preferably 20～35 quality % gets final product.In addition, also can be through being regardless of the heat treated at this so-called ashless coal of exsolution agent as the liquid portion direct heating that in above-mentioned solvent, extracts as the coal composition.Need to prove,, can use general distillation method or method of evaporation (spray-drying process etc.) etc. as the method for separating solvent the ashless coal after heat treated.
Through using solvent, to compare with the direct heating ashless coal, heat transfer efficiency improves, and can carry out uniform heating.In addition, through using and the solvent phase that in the modification of coal, uses solvent together, can reduce manufacturing cost.Need to prove,, can enumerate alkylnaphthalene and carbolineum etc. as preferred solvent as the solvent of the heat treated that is used for ashless coal.
< carbonation process >
Carbonation process is through the ashless coal after the heat treated in the above-mentioned ashless coal heating process is carried out the operation that carbonizing treatment obtains the raw material of wood-charcoal material.Through this carbonation process, ashless coal generation carbonization obtains the raw material of wood-charcoal material.
The method of carbonizing treatment and condition do not have special qualification, can use technique known.Be typically, in inert atmospheres such as nitrogen and argon gas, carry out heat treated through ashless coal is steamed down to burn at about 1000 ℃, thereby ashless coal is changed to carbon.In addition, heat-up rate can be about 0.1～5 ℃/minute.This carbonizing treatment can use heat isostatic apparatus etc. to carry out adding to depress.In addition, can add binder constituents such as pitch or tar as required.In addition, also can, the ashless coal after the heat treated carry out carbonation process after suitably being shaped.The form that is used for the heat treatment furnace of carbonization does not have special restriction yet, can use known heat treatment furnace.For example can enumerate: crucible oven, Li Dehanma (Riedhammer) stove, kiln, rotary kiln, shaft furnace or box-type furnace etc.But heat treatment furnace is not limited to these, also can use other heat treatment furnace.
In addition, the raw material of wood-charcoal material through method of manufacture of the present invention obtains can suitably use with anodic main raw material coke as the electrolysis of aluminum manufacturing.In addition; The raw material of wood-charcoal material that obtains among the present invention; In addition; Can also use with the raw material of wood-charcoal material with the electric material beyond the anode with raw material of wood-charcoal material or electrolysis of aluminum manufacturing as non-ferrous metal reductive agent, structure, perhaps, also can be used as non-ferrous metal reductive agent, structure and use with raw material of wood-charcoal material or electric material raw material with the raw material of wood-charcoal material.At this, the non-ferrous metal reductive agent is the reductive reductive agent that is used for non-ferrous metal such as silicon or titanium.In addition, structure is the raw material of wood-charcoal material that for example uses as the raw material of the structured material of carbon systems such as carbon system lagging material, crucible with the raw material of wood-charcoal material.In addition, electric material is as the raw material of wood-charcoal material of electrolysis of aluminum manufacturing with the raw material use of the electric material of carbon systems such as anode and carbon system electrode with the raw material of wood-charcoal material.Need to prove,, for example need implement secondary treatments such as thermal treatment sometimes the raw material of wood-charcoal material as the record that these raw materials use.
As above illustrated, the method for manufacture of raw material of wood-charcoal material of the present invention comprises: ashless coal manufacturing process, ashless coal heating process and carbonation process.But; When embodiment of the present invention; Above-mentioned each operation is not being produced in the dysgenic scope, during above-mentioned each operation or front and back for example can comprise: pulverize feed coal the broken operation of coal dust, remove rubbish etc. and do not need removing operation and making other operation such as ashless coal exsiccant ashless coal drying process of material.
Embodiment
Then, about the method for manufacture of raw material of wood-charcoal material of the present invention, enumerate embodiment, comparative example describes particularly.
[manufacturing of ashless coal]
At first, ashless coal is through following method manufacturing.
Feed coal be as bituminous coal coke production of raw material for use coal (coal A), or as the thermal power generation of bituminous coal with common coal (coal B).Through in this feed coal 5kg, mixing the solvent (1-methylnaphthalene (chemical company of Nippon Steel system)) of 4 times of amounts (20kg), prepare slurry.This slurry is pressurizeed under the nitrogen of 1.2MPa, in the autoclave of internal volume 30L, under 370 ℃, 1 hour condition, extract.This slurry is separated into supernatant and solids component liquid concentrator in the gravity sedimentation tank that keeps same temperature, pressure, from supernatant, separate, reclaim solvent, obtain ashless coal through distillation method.
[heat treated]
Then, ashless coal carries out heat treated through following method.
The heat treated of ashless coal, use with respect to ashless coal as solvent be 3 times of amounts (3 times in mass) 1-methylnaphthalene (chemical society of Nippon Steel system) condition or do not use fully under the condition of solvent and carry out.Heat treated is passed through in the autoclave of the air hermetic of nitrogen first pressing 0.1MPa, to stir in the ashless coal, and with 10 ℃ of/minute temperature that are warming up to the regulation shown in the table 1, and the specific time shown in the maintenance table 1 carries out.After the processing, discharge the gas in the autoclave, under the pressure of 0.001MPa, be heated to 150 ℃ 1 hour, thus, distillation remove desolvate with the oil content that possibly generate after, reclaim the ashless coal after the heat treated.In addition, through they are carried out ultimate analysis, obtain H/C atomicity ratio.
[carbonizing treatment]
Then, ashless coal carries out carbonizing treatment through following method.
Carrying out heat treated and be crushed in the ashless coal below the 1mm; 5g is filled in the quartzy developmental tube of internal diameter 20mm, makes volume density reach 0.8g/cc, then; Under the nitrogen mist, be warming up to 1000 ℃ with 3 ℃/minute; Keep carrying out carbonization in 30 minutes in this temperature, thus, obtain carbide (raw material of wood-charcoal material).
After the carbide that is generated cut into length 10mm, carry out crushing test, measure intensity.Crushing test is through load sample on the increased pressure board of bottom, utilizes top pressurization pressure head compression sample, and the intensity (crushing strength) when measuring the sample fragmentation is carried out.In addition, have the sample of the above intensity of 5.0MPa, be judged to be fine and close raw material of wood-charcoal material.Wherein, intensity changes according to the condition (having or not or thermal treatment temp of the pack density of raw material, shaping) of carbonizing treatment, and therefore, this numerical value is numerical value relatively eventually.Need to prove that it is finer and close to have a high-intensity raw material of wood-charcoal material, preferred with the coke raw material as anode.
This test-results of table 1 expression.Need to prove that in the table 1, the numerical value of discontented unabridged version scope of invention illustrates with underscore.In addition, the 1-methylnaphthalene is designated as MN in table.In addition, Fig. 1 is the figure of expression intensity and the relation of H/C atomicity ratio.Need to prove that therefore intensity " 0.00 " expression, can't carry out the mensuration of intensity owing to do not have the intensity that can measure.
[table 1]
Like table 1 and shown in Figure 1, scope of the present invention is satisfied in No.1～3,14～20.Therefore, these carry out carbonization and can not foam in carbonation process, obtain fine and close raw material of wood-charcoal material, and intensity is high.
On the other hand, No.4～6,21,22 H/C atomicity ratio are lower than lower value.Therefore, the raw material of wood-charcoal material becomes powdery, does not form fine and close raw material of wood-charcoal material, and intensity is low.Need to prove that the intensity of No.6 can't be measured.
In addition, No.7～13,23～25 H/C atomicity are than surpassing higher limit.Therefore, ashless coal produces foaming in the carbonation process, can not get fine and close raw material of wood-charcoal material, and intensity can't be measured.
More than, about the method for manufacture of raw material of wood-charcoal material of the present invention, embodiment is shown and embodiment at length is illustrated, but purport of the present invention being not limited to foregoing, its interest field must be explained based on the record of claims widely.Need to prove that content of the present invention is based on above-mentioned record, can change widely certainly, change etc.
The application is based on the Japanese patent application (Japan special hope 2009-147296) of application on June 22nd, 2009, and its content is introduced as reference at this.
Claims (2)
1. the method for manufacture of a raw material of wood-charcoal material, the method for manufacture of its raw material of wood-charcoal material that to be non-ferrous metal reductive agent, structure use with the raw material of wood-charcoal material or as their raw material with raw material of wood-charcoal material, electric material, wherein,
Comprise: ashless coal manufacturing process, use solvent that coal is carried out modification, make ashless coal thus as the modification coal; The ashless coal heating process is carried out heat treated to the said ashless coal of in said ashless coal manufacturing process, making; And carbonation process obtains the raw material of wood-charcoal material through the said ashless coal after the heat treated in said ashless coal heating process is carried out carbonizing treatment,
The hydrogen of the said ashless coal in said ashless coal heating process after the heat treated is 0.6～0.67 with the atomicity of carbon than H/C.
2. the method for manufacture of raw material of wood-charcoal material according to claim 1, wherein, in said ashless coal heating process, the heat treated of said ashless coal with said ashless coal manufacturing process in be used for said coal modification solvent phase with solvent in the presence of carry out.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-147296 | 2009-06-22 | ||
| JP2009147296A JP4660608B2 (en) | 2009-06-22 | 2009-06-22 | Carbon material manufacturing method |
| PCT/JP2010/060147 WO2010150685A1 (en) | 2009-06-22 | 2010-06-15 | Method for producing carbon materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102803136A true CN102803136A (en) | 2012-11-28 |
Family
ID=43386455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800275292A Pending CN102803136A (en) | 2009-06-22 | 2010-06-15 | Method For Producing Carbon Materials |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4660608B2 (en) |
| KR (1) | KR101365365B1 (en) |
| CN (1) | CN102803136A (en) |
| AU (1) | AU2010263737B2 (en) |
| CA (1) | CA2766032C (en) |
| WO (1) | WO2010150685A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105612245A (en) * | 2013-10-09 | 2016-05-25 | 株式会社神户制钢所 | Ashless coal production method |
| CN105765034A (en) * | 2013-12-04 | 2016-07-13 | 株式会社神户制钢所 | Method for producing coke, and coke |
| CN106715652A (en) * | 2014-10-07 | 2017-05-24 | 株式会社神户制钢所 | Method for deciding blending amount of ash-free coal, and process for producing coke for blast furnace |
| CN113583730A (en) * | 2021-06-29 | 2021-11-02 | 山西沁新能源集团股份有限公司 | High-carbon coke and preparation method of ultrapure coal for producing high-carbon coke |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012184125A (en) * | 2011-03-03 | 2012-09-27 | Kobe Steel Ltd | Method for producing carbon material |
| CN104685037B (en) * | 2012-09-26 | 2018-09-11 | 株式会社神户制钢所 | The manufacturing method of ashless coal |
| JP2014065823A (en) * | 2012-09-26 | 2014-04-17 | Kobe Steel Ltd | Production method of ashless coal |
| JP6199020B2 (en) * | 2012-10-12 | 2017-09-20 | 株式会社神戸製鋼所 | Production method of ashless coal |
| JP6017366B2 (en) * | 2013-04-16 | 2016-10-26 | 株式会社神戸製鋼所 | Production method of ashless coal |
| JP6017371B2 (en) * | 2013-04-26 | 2016-11-02 | 株式会社神戸製鋼所 | Ashless coal manufacturing method and carbon material manufacturing method |
| JP5982666B2 (en) * | 2013-12-25 | 2016-08-31 | 株式会社神戸製鋼所 | Production method of ashless coal |
| JP6174004B2 (en) * | 2014-12-08 | 2017-08-02 | 株式会社神戸製鋼所 | Carbon material manufacturing method |
| JP7134755B2 (en) * | 2018-07-10 | 2022-09-12 | 株式会社神戸製鋼所 | coke production method |
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- 2009-06-22 JP JP2009147296A patent/JP4660608B2/en not_active Expired - Fee Related
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- 2010-06-15 CA CA2766032A patent/CA2766032C/en not_active Expired - Fee Related
- 2010-06-15 WO PCT/JP2010/060147 patent/WO2010150685A1/en active Application Filing
- 2010-06-15 CN CN2010800275292A patent/CN102803136A/en active Pending
- 2010-06-15 KR KR1020117030586A patent/KR101365365B1/en active IP Right Grant
- 2010-06-15 AU AU2010263737A patent/AU2010263737B2/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5582789A (en) * | 1978-12-16 | 1980-06-21 | Kawasaki Steel Corp | Preparation of binder pitch for electrode |
| WO2008044728A1 (en) * | 2006-10-12 | 2008-04-17 | Kabushiki Kaisha Kobe Seiko Sho | Method for production of ashless coal |
| JP2009120464A (en) * | 2007-10-23 | 2009-06-04 | Kobe Steel Ltd | Method for producing carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105612245A (en) * | 2013-10-09 | 2016-05-25 | 株式会社神户制钢所 | Ashless coal production method |
| US9752088B2 (en) | 2013-10-09 | 2017-09-05 | Kobe Steel, Ltd. | Ashless coal production method |
| CN105612245B (en) * | 2013-10-09 | 2018-09-11 | 株式会社神户制钢所 | The manufacturing method of ashless coal |
| CN105765034A (en) * | 2013-12-04 | 2016-07-13 | 株式会社神户制钢所 | Method for producing coke, and coke |
| CN105765034B (en) * | 2013-12-04 | 2017-09-22 | 株式会社神户制钢所 | The manufacture method and coke of coke |
| CN106715652A (en) * | 2014-10-07 | 2017-05-24 | 株式会社神户制钢所 | Method for deciding blending amount of ash-free coal, and process for producing coke for blast furnace |
| CN113583730A (en) * | 2021-06-29 | 2021-11-02 | 山西沁新能源集团股份有限公司 | High-carbon coke and preparation method of ultrapure coal for producing high-carbon coke |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4660608B2 (en) | 2011-03-30 |
| JP2011001240A (en) | 2011-01-06 |
| KR20120026561A (en) | 2012-03-19 |
| CA2766032A1 (en) | 2010-12-29 |
| AU2010263737B2 (en) | 2013-01-31 |
| CA2766032C (en) | 2013-07-30 |
| KR101365365B1 (en) | 2014-02-24 |
| AU2010263737A1 (en) | 2012-01-19 |
| WO2010150685A1 (en) | 2010-12-29 |
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