CN102225755A - Preparation method of mesophase carbon microspheres from coal liquefaction residues - Google Patents
Preparation method of mesophase carbon microspheres from coal liquefaction residues Download PDFInfo
- Publication number
- CN102225755A CN102225755A CN 201110137897 CN201110137897A CN102225755A CN 102225755 A CN102225755 A CN 102225755A CN 201110137897 CN201110137897 CN 201110137897 CN 201110137897 A CN201110137897 A CN 201110137897A CN 102225755 A CN102225755 A CN 102225755A
- Authority
- CN
- China
- Prior art keywords
- mcmb
- coal liquefaction
- liquefaction residue
- prepares
- asphaltic bitumen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Working-Up Tar And Pitch (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of mesophase carbon microspheres from coal liquefaction residues serving as raw materials, which comprises the following steps of: firstly carrying out solvent extraction on the coal liquefaction residues, then carrying out a series of processing to obtain refined asphalt with different contents of quinoline insoluble substances, and carrying out thermal polycondensation reaction on the refined asphalt in the presence of a chemical auxiliary agent and a nucleating accelerator at the temperature of 380-450 DEG C, the pressure of 0-5 MPa and the stirring rotation speed of 40-500 r/min for 1-20 hours to obtain the mesophase microspheres. According to the invention, the chemical auxiliary agent and the nucleating accelerator can be added during the heat treatment process to improve the yield and narrow the particle size distribution of the mesophase carbon microbeads, and the mesophase carbon microspheres are prepared from the coal liquefaction residues serving as the raw materials and have the advantages of low cost, simple preparation process, high yield (up to 35%), narrow particle size distribution, good sphericity, etc.
Description
Technical field
Coal liquefaction residue prepares the method for MCMB, relates to coal deep processing field, particularly relates to the method for using residue after the gelatin liquefaction to prepare MCMB.
Background technology
MCMB (MCMB) is a kind of novel charcoal material, and it can be used for preparing electrode material of secondary lithium ion battery, high-density and goods such as high-intensity various graphite or carbon material.MCMB is that discovery, the researchdevelopment along with mesophase pitch got up.1961, Taylor found to have in vitrain the different microsphere of some optics to produce, grow up when the research coal tar and melts phenomenon also, has finally generated pattern structure.In fact, the microsphere of these anisotropics is exactly MCMB.By 1973, people isolated MCMB from liquid phase charing pitch, and began to utilize spherocrystal to make binder free respectively to the homogeny high density material.
MCMB normally pitch class organic compound such as petroleum residual oil and coal-tar pitch is heat-treated in about 350～550 ℃ of middle temperature, inert atmosphere, the molecular weight that forms gradually through series of chemical such as pyrolysis, dehydrogenation and polycondensations is big, planeness is higher, thermodynamically stable condensation condensed-nuclei aromatics, and the diameter that aligns the self-assembly generation under capillary effect is each different in nature spheroidal aggravation of optics of 5～100 μ m.It is the middle mesomorphic state of the pitch class organic compound of liquid state to the solid carbon transit time, so be called carbonaceous mesophase phase or carbonaceous liquid crystal again.
The preparation of MCMB is guidance with liquid phase charing theory.In the liquid phase carbonization process, constantly carry out the reaction of pyrolysis and thermal polycondensation in the liquid-phase reaction system, the isotropy liquid phase becomes anisotropic mesophasespherule gradually, and along with the raising of anisotropy degree, mesophasespherule has experienced generation, the process of disintegration and carbon structure formation of melting also, grow up.According to liquid phase charing theory, the difficulty or ease of each liquid-like phase charing are followed successively by polycyclic aromatic hydrocarbons, aromatic hydrocarbons, alkene and alkane by order from easy to difficult.Therefore, preparation MCMB ear raw material mostly is the hydro carbons that contains the polycyclic aromatic hydrocarbons heavy ingredient.The generation of mesophasespherule, grow up, melt and and the influence factor of structure material viscosity under composition (as pyridine insoluble PI amount, quinoline insolubles QI amount), additional substance (as carbon black, Graphite Powder 99, coke powder and organometallic compound etc.) and the temperature of reaction of raw material etc. is arranged.Wherein the QI of quinoline insolubles amount is in close relations to the preparation of intermediate.Add other materials in the raw material preparation MCMB is had remarkable influence.People such as Song Huaihe add carbon black in the catalytic cracking residual oil of preparation MCMB, proof adds the formation that carbon black can promote the MCMB ball, and melting also between the prevention microballoon, and the carbon black add-on also has material impact to MCMB diameter, quantity, distribution and productive rate.Add graphite and also have same effect.Adding organometallic compound such as ferrocene in the raw material also can effectively promote spherular even generation and stop it to melt also.
The method for preparing MCMB is a lot, but generally all pass through following step: at first raw material is through the thermal polycondensation reaction, prepare and contain that mesophase ball or intermediate phase melt and the mesophase pitch of body, and then be further processed and prepare the single mesophase ball with asphalt characteristic, be referred to as the mesophase pitch carbon microspheres.Hot polymerization is legal to have that technology is simple, facility investment is few and reaction is easy to characteristics such as control.Direct polycondensation method is the method that adopts the earliest, and it is to become mesophase ball in the direct charing of the following material asphalt of inert atmosphere (as nitrogen), by the thermal polycondensation reaction, prepares the pitch that contains mesophase ball.Also having another kind of is indirect method (comprising emulsion process, suspension method etc.).Emulsion process proposed in 1988, and its main idea is to be that quinoline solubility mesophase pitch about 300 ℃ is pulverized and is dissolved in the silicone oil with softening temperature, and heated and stirred becomes milk sap, and cooling then, centrifugation are also cleaned with benzene, just obtain MCMB after the drying.Suspension method is that the solubility mesophase pitch is dissolved in the solvent, makes it form suspension under tensio-active agent, and powerful the stirring made the mesophase pitch bead under the certain temperature then, and reheat, cooling, filter are analysed, charing etc. finally makes MCMB.Direct polycondensation method and indirect method are compared, and the former can add additive usually in order to improve yield, but this method technology is simple, cost is lower.Indirect method, the technology of for example emulsification legal system MCMB is had relatively high expectations to heat stable dielectric, and the MCMB that makes is gone to toward carrying out not melt processed of oxidation, so that make it keep certain shape and structure in carbonization process in charing.Emulsion process complicated process of preparation, process are loaded down with trivial details, so the preparation MCMB generally adopts low cost, the simple direct polycondensation method of technology.Chinese patent CN1197833 for example, adopting coal tar mixing black petroleum products is that raw material carries out thermal polycondensation and prepares MCMB.It is raw material that Japanese Patent 7968/1989 (JP-1-27968B) adopts coal tar, handles under certain pressure, and again through Overheating Treatment, classification obtains MCMB of appropriate particle size or the like later on.
In addition on the one hand, China's primary energy source characteristics of resources is " many coals, few oil, a scarce Sweet natural gas ".China be transformed into from oil exportiog countries be provided with, Sweet natural gas import big country.Along with the increase of global oil extraction and the minimizing of reserves, the breach of oil supply is increasing, thereby make full use of the abundant in coal resource, it is the risk that diversification reduces oil supply that the degree of depth of greatly developing product of coal is utilized technology, an important channel of realizing the energy, economy, harmonious development.In the DCL/Direct coal liquefaction production process, employ direct coal liquefaction technology no matter, no matter adopt which kind of solid-liquid separating method (underpressure distillation, solvent extraction and filtration), the inorganic mineral that is mingled with in certain unreacted coal, the coal is always arranged and add the solid materials such as catalyzer of coal slurry and the intermediate product of some gelatin liquefactions is discharged liquefying plant together.Surplus materials after the parting liquid carburetion is called liquefied residue, and it is a kind of high-carbon, high ash and doctor positive material, and output generally reaches about 30% of feed coal.So still be that environmental angle is considered no matter, all be the important component part of coal liquefaction craft exploitation to the utilization research of residue from economy.For example: it is the feedstock production carbon nano-material that Chinese patent 200510047800.X discloses with the coal liquefaction residue; It is the raw material production road asphalt modifier that Chinese patent 200610012547.9 discloses with the coal liquefaction residue; Patent 200910086158.4 is a raw material with the coal liquefaction residue, direct production body mesophase pitch, and simultaneously, this patent has also hinted the potentiality that coal liquefaction residue is produced the intermediate phase product.
Usually direct heat is handled the MCMB distribution of sizes broad that the back generates, and yield is lower.Having grown up thus, some prepare the improvement technology of MCMB, and Chinese patent CN1278513A openly adopts the itrated compound that adds iron, nickel, cobalt in MCMB to improve the productive rate of MCMB and the size distribution that narrows; Patent CN101721966 regulates and control the particle diameter of MCMB by the rotating speed of control stirring rake; Patent CN101184825A carries out blend by choosing two kinds of different material asphalts of aromatic carbon content, prepares high yield and ganoid MCMB; It is raw material that patent CN101811691 adopts coal-tar pitch, thermopolymerization generates mesophase ball, but when extracting bead, adopt adding anion surfactant and washing oil waits and produces narrow size distribution and sphericity mesophase ball preferably, this method has been avoided the use of a large amount of polar solvents such as pyridine, quinoline etc., helps reducing cost; U.S. Pat 4381990 adopts two step method of cooling to come the homogenizing crystallisation process, makes the mesophase ball that generates have narrow size distribution.The technical scheme of these patent disclosures is all being carried out improvement to a certain degree aspect the raising MCMB quality, but none relates to the method for utilizing coal liquefaction residue to prepare MCMB.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, providing a kind of is raw material with coal liquefaction residue cheaply, and technology is simple, product yield is high and the coal liquefaction residue of gained MCMB (MCMB) narrow diameter distribution, good sphericity prepares the method for MCMB.
The technical scheme that technical solution problem of the present invention is taked is: coal liquefaction residue prepares the method for MCMB, it is characterized in that comprising following preparation process:
A, preparation refined asphaltic bitumen: at first coal liquefaction residue is dried to moisture mass content≤3%, added extraction agent in 1: 3～1: 8 to wherein pressing mass ratio, stir under 20～60min normal temperature and extract, separate by centrifugation again and remove insolubles, gained extraction liquid reduction vaporization more than 2 hours under 200～300 ℃ of temperature, pressure≤0.2atm obtains quinoline insolubles content and is 0.1～1% refined asphaltic bitumen;
B, preparation mesophase ball: in the refined asphaltic bitumen that step a obtains, add the chemical assistant of refined asphaltic bitumen quality 0.01～5% and 0.1～6% nucleation accelerating agent, at 380～450 ℃ of temperature of reaction, pressure 0～5MPa, thermal polycondensation reaction 1～20h makes mesophase ball under mixing speed 40～500r/min;
C, washing, separation and dry: the mesophase ball that step b is made uses the cleaning solvent washing for several times, filters and oven dry, obtains MCMB.
Extraction agent described in the step a comprise in toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, pyridine, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, dimethyl formamide, the dithiocarbonic anhydride a kind of, two or more.
Centrifugation described in the step a adopts whizzer to separate, centrifuge speed has a lower limit to control the content of quinoline insolubles, difference according to the whizzer kind, minimum speed is also different, rotating speed 〉=the 4800r/min of the whizzer of this experiment strip adoption, being generally is 4800～7000r/min.
Preferably, the reaction pressure described in the step b is 0～3MPa, and the reaction times is 1～15h, and stirring velocity is 100～400r/min.
More preferably, the described reaction pressure of step b is 0.5～2MPa, and the reaction times is 3～10h, and stirring velocity is 200～300r/min.
Chemical assistant described in the step b comprises aluminum chloride, pyridine alkane boron, resol, polystyrene, polyoxymethylene, iron, nickel, the muriate of cobalt, itrated compound or oxide compound, para benzoquinone, HEXACHLOROBUTADIENE, boron trifluoride/ether complex, in the para benzoquinone one or more, consumption are 0.05～4% of refined asphaltic bitumen quality.
Nucleation accelerating agent described in the step b comprises one or more in Graphite Powder 99, thin mica powder, carbon black pellet, alumina particle, kaolin, nano level coke powder, nanometer grade silica, nano zircite, the nano-calcium carbonate, and consumption is 0.5～4% of a refined asphaltic bitumen quality.
Further, the consumption of described chemical assistant is 0.05～2.4% of a refined asphaltic bitumen quality.
Further, the consumption of described nucleation accelerating agent is 1.5～3% of a refined asphaltic bitumen quality.
Cleaning solvent described in the step c comprises one or more in washing oil, middle oil, carbolineum, toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, quinoline, pyridine, tetrahydrofuran (THF) and the N,N-DIMETHYLACETAMIDE.
MCMB is a kind of carbonaceous liquid crystal material, generally by coal-tar pitch or petroleum pitch preparation.Because having unique molecule aspect parallel stacks, it builds structure, have ganoid ball nature again concurrently, become the preferred material of the packing material etc. of electrode material of secondary lithium ion battery, high-density isotropic charcoal graphite block material, high-ratio surface microsphere active carbon and high performance liquid chromatography.
Usually, MCMB adopts coal-tar pitch or petroleum pitch to prepare.Among the present invention, adopt cheaply that coal liquefaction residue is a raw material, wherein reactive big by removing, the high molecular weight material that content of heteroatoms is high obtains reactive moderate refined asphaltic bitumen product and carries out heat polymerization production MCMB.In the coal liquefaction residue, the reactive behavior of some high molecular weight materials is higher, can make that liquid phase carburizing reagent religion is fast, be difficult to obtain the mesophase ball of even size distribution, by extracting and ultracentrifugal method the molecular weight distribution that can regulate whole asphaltic products., content of heteroatoms, parameters such as heavy metal content, thus obtain preparing the raw material of high-quality MCMB product.By nuclear magnetic resonance spectroscopy, this refined asphaltic bitumen contains a large amount of naphthenic hydrocarbon structures, and this constructional feature makes the relative coal-tar pitch of its speed of response or petroleum pitch faster.And because the overall molecule amount is bigger than normal, when adding chemical assistant, though the productive rate of bead is improved, whole system causes bead size lack of homogeneity because generation, the system viscosity of crosslinking reaction increase fast.The employing chemical assistant should be controlled the crosslinking reaction between the component, also will promote the polycondensation between the phenyl ring simultaneously.Like this, whole reaction system is in generating the process of mesophase ball, and it is too high and influence the distribution of bead particle diameter to be unlikely to viscosity.The kind of chemical assistant can be AlCl
3, pyridine alkane boron, resol, elementary sulfur, polystyrene, polyoxymethylene, Fe, Ni, the muriate of Co or itrated compound or oxide compound, para benzoquinone, HEXACHLOROBUTADIENE, boron trifluoride/ether complex, para benzoquinone etc.Single chemical assistant can be adopted, also the number of chemical auxiliary agent can be adopted.The consumption of chemical assistant can 0.01～5%, is preferably 0.05～4%, and more excellent is 0.05～2%.
Coal liquefaction residue is by disclosed treatment process among the present invention, can obtain different quinoline insolubles content or not contain the refined asphaltic bitumen of quinoline insolubles.In general, in the mesophase ball production process, need quinoline insolubles to come nucleation and prevent bead melt and, but in this refined asphaltic bitumen production process, the rotating speed of whizzer to the content of quinoline insolubles with and size tangible influence is arranged, centrifugal rotational speed is lower than under the situation of some numerical value (this experiment whizzer is 4800r/min), and the QI content that obtains is higher and particle diameter is bigger.High QI content can reduce the chemical property of MCMB, and bigger QI particle diameter can cause being suppressed in the nucleation promoter action of QI in heat polymerization process.So we are by the centrifugal pitch that at first obtains low QI content, and then the interpolation nucleation accelerating agent substitutes the effect of primary quinoline insolubles in the pitch.Nucleation accelerating agent can be a Graphite Powder 99, thin mica powder, carbon black pellet, alumina particle, kaolin, nano level coke powder, nanometer grade silica, nano zircite, nano-calcium carbonate etc.The usage quantity of nucleation accelerating agent can be 0.1～6%, preferably 0.5～4%, and more excellent is 1～3%.
In the heat polymerization process of phase bead, reaction can be normal pressure or pressurization aborning, and pressure can be 0～5MPa, is preferably 0～3MPa, more preferably 0.5～2MPa.Pressurization can increase productive rate usually, reduces whole system viscosity simultaneously.
In addition, can come heat treatment time is carried out appropriate selection according to the difference of chemical additive and the difference of pressure.Heat treatment time can be 1～20h, is preferably 1～15h, and more excellent is 3～10h.
In order to make the system homogenization, in heat treatment process, adopt stirring rake usually.Wherein optimum stirring velocity is according to the difference of stirring rake design.If the system viscosity is bigger, also can adopt high rotational speed.Stirring velocity can be 40～500r/min, is preferably 100～400r/min, and more excellent is 200～300r/min.
After heat polymerization is finished,, separate isotropic pitch and MCMB again by suitable solvent wash.The selection of cleaning solvent can be a washing oil, middle oil, and carbolineum, perhaps organic solvent, as toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, quinoline, pyridine, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE etc.Different solvent treatment, the bead configuration of surface of acquisition is differentiated.Obtain the MCMB product by drying at last, the productive rate of carbon microspheres is 10～35%.
In MCMB, contain usually some diameters less than 2 μ m once or the secondary quinoline insolubles, these materials can reduce loading capacity or initial stage efficient.The diameter that MCMB among the present invention contains is not more than 6% less than the particle of 2 μ m, preferably is not more than 5%, more excellently is not more than 3%.The reason that finely ground particle substance is few is consistent with the nmr analysis result, the cycloalkanes structure that promptly contains in the pitch, the carbon microspheres surface free energy that make to generate is lower, thus in the forming process of MCMB, cause to short grained adsorptive power a little less than.
Compared with prior art, the beneficial effect that method had that coal liquefaction residue of the present invention prepares MCMB is: the present invention's gelatin liquefaction waste residue cheaply utilizes again, technology is simple, the MCMB productive rate that obtains is 10～35%, narrow diameter distribution, the ball smooth surface, good sphericity.
Description of drawings
Fig. 1 is intermediate phase charcoal coal briquette (MCMB) the size distribution figure of gained of the present invention.
Fig. 2 is scanning electronic microscope (SEM) photo of gained intermediate phase charcoal coal briquette of the present invention (MCMB).
The present invention will be further described below in conjunction with accompanying drawing 1～2:
Embodiment
Embodiment 1
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue be 1: 3～4 add in toluene, dimethylbenzene, the dimethyl sulfoxide (DMSO) a kind of, two or more, stirring 20min extracts, centrifugation and remove insolubles under rotating speed 4800～7000r/min again, remove the extraction phase reduction vaporization 4h under 200～220 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.5% quinoline insolubles, its softening temperature is 92 ℃;
B, the nucleation accelerating agent that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 2% and 0.7% chemical assistant.Be heated to the above temperature of softening temperature, mix chemical assistant and nucleation accelerating agent then.The thermal polycondensation reaction 5～8h under 380～400 ℃ and mixing speed 450～500r/min, the normal pressure that then heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected nano silicon for use, and the cobalt oxide that accounts for refined asphaltic bitumen quality 0.2% and 0.5% ferric oxide are selected in the chemical assistant agent for use.
C, washing, separation are also dry: oil and tetrahydrofuran (THF) washing several during the mesophase ball that step b is made uses, and filtering separation is also carried out drying, obtains MCMB, and productive rate is 25%.
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue be 1: 4～5 add in N-Methyl pyrrolidone, quinoline, the pyridine a kind of, two or more, stir 30～40min and extract, under rotating speed 4800～7000r/min, separate again and remove insolubles.Remove the extraction phase reduction vaporization 5h under 220～240 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.1% quinoline insolubles, its softening temperature is 101 ℃.
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 1.3% and 1% nucleation accelerating agent.Be heated to the above temperature of softening temperature, mix chemical assistant and nucleation accelerating agent then.The thermal polycondensation reaction 8～10h under 400～420 ℃, 2MPa and the mixing speed 180～200r/min that then heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected Graphite Powder 99 for use, and chemical assistant comprises the cobalt chloride that accounts for refined asphaltic bitumen quality 0.3% and 1% polystyrene.
C, washing, separation and dry: the mesophase ball that step b is made uses carbolineum and N-Methyl pyrrolidone to wash for several times, and filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 26%.
Embodiment 3
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 5～6 to add one or both (mass ratio of tetrahydrofuran (THF) and N,N-DIMETHYLACETAMIDE is 4: 6 when selecting two kinds simultaneously for use) in tetrahydrofuran (THF)s, the N,N-DIMETHYLACETAMIDE, stir 30～40min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 230～250 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.1% quinoline insolubles, its softening temperature is 92 ℃.
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 1.8% and 1.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 10～12h under 420～440 ℃, 4MPa and the mixing speed 40～50r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected thin mica powder for use, and chemical assistant comprises the nickelous nitrate that accounts for refined asphaltic bitumen quality 0.3% and 1.5% polyoxymethylene.
C, washing, separation and dry: with mesophase ball washing oil and dimethyl formamide washing several that step b makes, filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 22%.
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 5～6 to add one or both (mass ratio of dimethyl formamide and dithiocarbonic anhydride is 6: 4 when selecting two kinds simultaneously for use) in dimethyl formamides and the dithiocarbonic anhydride, stir 50～60min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 250～270 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.4% quinoline insolubles, its softening temperature is 91 ℃.
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 1.3% and 1.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 10～12h under 440～450 ℃, 2MPa and the mixing speed 50～60r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected alumina particle and kaolin (aluminum oxide and kaolinic mass ratio are 4: 6) for use, and chemical assistant comprises the nickelous chloride that accounts for refined asphaltic bitumen quality 0.3% and 1% HEXACHLOROBUTADIENE.
C, washing, separation and dry: the mesophase ball that step b is made washs for several times through washing oil and quinoline, and filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 22%.
Embodiment 5
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 7～8 to add one or both (mass ratio of dimethyl formamide and dithiocarbonic anhydride is 6: 4 when selecting two kinds simultaneously for use) in dimethyl formamides and the dithiocarbonic anhydride, stir 50～60min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 280～300 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.4% quinoline insolubles, its softening temperature is 91 ℃.
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 1.2% and 1.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 14～15h under 440～450 ℃, 0.5MPa and the mixing speed 220～230r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected nano zircite or nano-calcium carbonate for use, and chemical assistant comprises the boron trifluoride/ether that accounts for refined asphaltic bitumen quality 0.2% and 1% polyoxymethylene.
C, washing, separation and dry: the mesophase ball that step b is made washs for several times through dimethylbenzene or dimethyl sulfoxide (DMSO), and filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 30%.
Embodiment 6
This coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 5～6 to add one or both (mass ratio of dimethyl formamide and N-Methyl pyrrolidone is 5: 5 when selecting two kinds simultaneously for use) in dimethyl sulfoxide (DMSO) and the N-Methyl pyrrolidone, stir 30～40min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 250～260 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.1% quinoline insolubles, its softening temperature is 97 ℃.
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 2.4% and 1.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 6～9h under 400～420 ℃, 1.5MPa and the mixing speed 250～260r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected nano level coke powder for use, and chemical assistant comprises the iron(ic) chloride that accounts for refined asphaltic bitumen quality 0.4% and 2% resol.
C, washing, separation and dry: the mesophase ball that step b is made washs for several times through tetrahydrofuran (THF) and pyridine, and filtering separation is also dry, obtains MCMB.The productive rate of MCMB is 35%.
Products obtained therefrom is detected with instrumental analysis, and its size distribution figure and scanning electronic microscope (SEM) photo is seen Fig. 1 and Fig. 2 respectively.As seen from the figure, gained MCMB size distribution is narrower, and particle surface is smooth, and each is different to character, and the productive rate of MCMB is a preferred forms of the present invention up to 35% in this example.
Embodiment 7
A kind of coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 5～6 to add one or both in dithiocarbonic anhydride and the pyridine, stir 30～40min and extract, under rotating speed 4800～7000r/min, separate again and remove insolubles.Remove the extraction phase reduction vaporization 5h under 220～230 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.4% quinoline insolubles, its softening temperature is 96 ℃;
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 0.7% and 1.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 7～8h under 400～420 ℃, 1.5MPa and the mixing speed 250～260r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected nano level coke powder for use, and chemical assistant comprises aluminum chloride and 0.2% nickelous nitrate that accounts for refined asphaltic bitumen quality 0.5%.
C, washing, separation and dry: the mesophase ball that step b is made washs for several times through tetrahydrofuran (THF) and N,N-DIMETHYLACETAMIDE, and filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 32%.
Embodiment 8
A kind of coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 7～8 to add dimethyl sulfoxide (DMSO), stir 30～40min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 220～230 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 0.5% quinoline insolubles, its softening temperature is 97 ℃;
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 4% and 0.5% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 1～3h under 400～420 ℃, 2MPa and the mixing speed 220～230r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected nano level coke powder for use, and chemical assistant comprises para benzoquinone and 0.4% cobalt oxide that accounts for refined asphaltic bitumen quality 0.1%.
C, washing, separation are also dry: the mesophase ball that step b is made through carbolineum or toluene wash for several times, filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 10%.
Embodiment 9
A kind of coal liquefaction residue prepares the method for MCMB to be finished according to the following steps:
A, with coal liquefaction residue dry to moisture content below 3%, to wherein by quality than extraction agent: coal liquefaction residue is 1: 7～8 to add pyridine, tetrahydrofuran (THF) and N,N-DIMETHYLACETAMIDEs, wherein the ratio of quality and the number of copies of pyridine, tetrahydrofuran (THF) and N,N-DIMETHYLACETAMIDE is 1: 4: 5, stir 30～40min and extract, centrifugation and remove insolubles under rotating speed 4800～7000r/min again.Remove the extraction phase reduction vaporization 5h under 220～230 ℃ of temperature, pressure≤0.2atm behind the insolubles, obtain containing the refined asphaltic bitumen of 1.0% quinoline insolubles, its softening temperature is 95 ℃;
B, the chemical assistant that in the refined asphaltic bitumen that step a obtains, adds refined asphaltic bitumen quality 0.05% and 4% nucleation accelerating agent.Be heated to the above temperature of softening temperature, then exquisite pitch and chemical assistant and nucleation accelerating agent mixed.The thermal polycondensation reaction 3～4h under 400～420 ℃, 2MPa and the mixing speed 220～230r/min that heats up makes mesophase ball.Wherein, nucleation accelerating agent is selected kaolin for use, and chemical assistant comprises para benzoquinone and the 0.04% pyridine alkane boron that accounts for refined asphaltic bitumen quality 0.01%.
C, washing, separation are also dry: the mesophase ball that step b is made through carbolineum or toluene wash for several times, filtering separation is also carried out drying, obtains MCMB.The productive rate of MCMB is 15%.
The above only is preferred embodiment of the present invention, is not to be the restriction of invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (10)
1. a coal liquefaction residue prepares the method for MCMB, it is characterized in that comprising following preparation process:
1.1, the preparation refined asphaltic bitumen: at first coal liquefaction residue is dried to moisture mass content≤3%, added extraction agent in 1: 3～1: 8 to wherein pressing mass ratio, stir under 20～60min normal temperature and extract, separate by centrifugation again and remove insolubles, the gained extraction liquid is reduction vaporization under 200～300 ℃ of temperature, pressure≤0.2atm, obtains quinoline insolubles content and be 0.1～1% refined asphaltic bitumen;
1.2, the preparation mesophase ball: in the refined asphaltic bitumen that step 1.1 obtains, add and account for the chemical assistant of refined asphaltic bitumen quality 0.01～5% and 0.1～6% nucleation accelerating agent, 380～450 ℃ of temperature of reaction, pressure 0～5MPa, thermal polycondensation reaction 1～20h makes mesophase ball under mixing speed 40～500r/min;
1.3, washing, separate and dry: the mesophase ball that step 1.2 is made uses the cleaning solvent washing for several times, filters also oven dry, obtains MCMB.
2. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the extraction agent described in the step 1.1 is one or more in toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, pyridine, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, dimethyl formamide, the dithiocarbonic anhydride.
3. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the centrifugation described in the step 1.1 adopts whizzer to separate, and the rotating speed of whizzer is 4800～7000r/min.
4. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the reaction pressure described in the step 1.2 is 0～3MPa, and the reaction times is 1～15h, and stirring velocity is 100～400r/min.
5. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the reaction pressure described in the step 1.2 is 0.5～2MPa, and the reaction times is 3～10h, and stirring velocity is 200～300r/min.
6. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the chemical assistant described in the step 1.2 comprises aluminum chloride, pyridine alkane boron, resol, polystyrene, polyoxymethylene, iron, nickel, the muriate of cobalt, itrated compound or oxide compound, para benzoquinone, HEXACHLOROBUTADIENE, boron trifluoride/ether complex, in the para benzoquinone one or more, consumption are 0.05～4% of refined asphaltic bitumen quality.
7. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the nucleation accelerating agent described in the step 1.2 comprises one or more in Graphite Powder 99, thin mica powder, carbon black pellet, alumina particle, kaolin, nano level coke powder, nanometer grade silica, nano zircite, the nano-calcium carbonate, consumption is 0.5～4% of a refined asphaltic bitumen quality.
8. coal liquefaction residue according to claim 6 prepares the method for MCMB, and the consumption that it is characterized in that described chemical assistant is 0.05～2.4% of a refined asphaltic bitumen quality.
9. coal liquefaction residue according to claim 7 prepares the method for MCMB, and the consumption that it is characterized in that described nucleation accelerating agent is 1.5～3% of a refined asphaltic bitumen quality.
10. coal liquefaction residue according to claim 1 prepares the method for MCMB, it is characterized in that the cleaning solvent described in the step 1.3 comprises one or more in washing oil, middle oil, carbolineum, toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, quinoline, pyridine, tetrahydrofuran (THF) and the N,N-DIMETHYLACETAMIDE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110137897 CN102225755B (en) | 2011-05-26 | 2011-05-26 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110137897 CN102225755B (en) | 2011-05-26 | 2011-05-26 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102225755A true CN102225755A (en) | 2011-10-26 |
| CN102225755B CN102225755B (en) | 2013-02-27 |
Family
ID=44806769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110137897 Expired - Fee Related CN102225755B (en) | 2011-05-26 | 2011-05-26 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102225755B (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
| CN102676195A (en) * | 2012-05-23 | 2012-09-19 | 徐国财 | Chemical modification method of coal pitch with unsaturated thermoplastic elastomer |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| CN103326024A (en) * | 2013-06-14 | 2013-09-25 | 苏州诺信创新能源有限公司 | Preparation method of intermediate phase graphite for lithium-ion battery negative material |
| CN103613089A (en) * | 2013-11-29 | 2014-03-05 | 神华集团有限责任公司 | Method of preparing mesocarbon microbeads by coal liquefaction residues and mesocarbon microbeads |
| CN103614153A (en) * | 2013-11-29 | 2014-03-05 | 神华集团有限责任公司 | Preparation method of polycondensed asphalt, preparation method of needle coke and needle coke |
| CN104031669A (en) * | 2013-03-07 | 2014-09-10 | 神华集团有限责任公司 | Electrode pitch and preparation method thereof |
| CN105720233A (en) * | 2014-12-04 | 2016-06-29 | 神华集团有限责任公司 | Carbon material for lithium ion battery negative electrode and preparation method for carbon material, lithium ion battery negative electrode and lithium ion battery |
| CN105838409A (en) * | 2015-01-12 | 2016-08-10 | 神华集团有限责任公司 | Method for preparing mesophase pitch from residues of coal liquefaction and prepared mesophase pitch |
| CN105838408A (en) * | 2015-01-12 | 2016-08-10 | 神华集团有限责任公司 | Method for preparing mesophase pitch from residue derived from coal liquefaction and prepared mesophase pitch |
| CN105905883A (en) * | 2016-04-15 | 2016-08-31 | 神华集团有限责任公司 | Mesocarbon microbead and preparation method thereof |
| CN106497591A (en) * | 2016-10-21 | 2017-03-15 | 湖南大学 | A kind of preparation method for catalyzing and synthesizing mesophase pitch |
| CN106753495A (en) * | 2016-12-29 | 2017-05-31 | 中石化南京工程有限公司 | A kind of method of high temperature coal-tar/residual oil production carbosphere and dipping agent bitumen |
| CN106811235A (en) * | 2016-12-29 | 2017-06-09 | 中石化南京工程有限公司 | A kind of device and method of mink cell focus/residual oil/coal tar catalytic cracking polymerisation lighting |
| CN107021471A (en) * | 2017-05-31 | 2017-08-08 | 中国科学院山西煤炭化学研究所 | A kind of method that medium temperature coal pitch prepares MCMB |
| CN108258242A (en) * | 2016-12-28 | 2018-07-06 | 上海宝钢化工有限公司 | Preparation method of high-performance artificial graphite anode material precursor |
| CN108485694A (en) * | 2018-04-11 | 2018-09-04 | 北京化工大学 | A method of carbonizatin method prepares high-quality mesophase pitch altogether |
| CN108611114A (en) * | 2018-05-31 | 2018-10-02 | 山西豪仑科化工有限公司 | A kind of method of coal liquifaction dregs of fat extraction |
| CN109082292A (en) * | 2018-09-04 | 2018-12-25 | 福建海峡能源集团股份有限公司 | A kind of technique for extracting pitch from putty slag |
| CN109504416A (en) * | 2018-12-04 | 2019-03-22 | 大同新成新材料股份有限公司 | A kind of production technology of coal-based needle coke |
| CN109504415A (en) * | 2018-12-04 | 2019-03-22 | 大同新成新材料股份有限公司 | A kind of production method of needle coke |
| CN110357089A (en) * | 2019-06-24 | 2019-10-22 | 鞍钢股份有限公司 | Method for cleaning carbon microspheres by using N, N-dimethyl formamide |
| CN110499175A (en) * | 2019-09-04 | 2019-11-26 | 北京旭阳科技有限公司 | A method of super regular high-purity pitch coke is prepared by mid temperature pitch |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| CN111547715A (en) * | 2020-04-28 | 2020-08-18 | 鞍钢股份有限公司 | Method for improving yield of mesocarbon microbeads |
| CN112642417A (en) * | 2020-12-10 | 2021-04-13 | 西安凯立新材料股份有限公司 | Preparation method and application of dehydrogenation catalyst carrier |
| CN112831334A (en) * | 2021-01-13 | 2021-05-25 | 中国石油大学(华东) | Preparation method of mesophase pitch and mesophase carbon microspheres |
| CN113247878A (en) * | 2021-06-30 | 2021-08-13 | 北京化工大学 | Preparation method and application of asphalt-based carbon microspheres |
| CN113508169A (en) * | 2019-03-04 | 2021-10-15 | 杰富意钢铁株式会社 | Method for evaluating coal, method for producing coal blend, and method for producing coke |
| CN113667506A (en) * | 2020-05-15 | 2021-11-19 | 中国石油化工股份有限公司 | Preparation method and preparation system of mesophase pitch |
| CN114477126A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Mesocarbon microbeads and preparation method thereof |
| CN115521802A (en) * | 2022-09-16 | 2022-12-27 | 北京化工大学 | Method for preparing mesophase pitch by catalysis of cocatalyst-Lewis acid system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259546A (en) * | 1999-01-04 | 2000-07-12 | 北京化工大学 | Prepn. method of mesophase asphalt carbon microsphere |
| CN1272453A (en) * | 2000-05-26 | 2000-11-08 | 冶金工业部鞍山热能研究院 | Preparation method of mesophase carbon microsphere |
| CN1607237A (en) * | 2003-10-16 | 2005-04-20 | 淄博矿业集团有限责任公司许厂煤矿 | Method for preparing refined coal tar |
| CN101580729A (en) * | 2009-06-11 | 2009-11-18 | 煤炭科学研究总院 | Method for preparing mesophase asphalt by coal liquefaction residue |
| CN101811691A (en) * | 2010-04-23 | 2010-08-25 | 上海应用技术学院 | Preparation method of mesocarbon microbead |
-
2011
- 2011-05-26 CN CN 201110137897 patent/CN102225755B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259546A (en) * | 1999-01-04 | 2000-07-12 | 北京化工大学 | Prepn. method of mesophase asphalt carbon microsphere |
| CN1272453A (en) * | 2000-05-26 | 2000-11-08 | 冶金工业部鞍山热能研究院 | Preparation method of mesophase carbon microsphere |
| CN1607237A (en) * | 2003-10-16 | 2005-04-20 | 淄博矿业集团有限责任公司许厂煤矿 | Method for preparing refined coal tar |
| CN101580729A (en) * | 2009-06-11 | 2009-11-18 | 煤炭科学研究总院 | Method for preparing mesophase asphalt by coal liquefaction residue |
| CN101811691A (en) * | 2010-04-23 | 2010-08-25 | 上海应用技术学院 | Preparation method of mesocarbon microbead |
Cited By (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491307B (en) * | 2011-11-25 | 2014-07-23 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
| CN102676195A (en) * | 2012-05-23 | 2012-09-19 | 徐国财 | Chemical modification method of coal pitch with unsaturated thermoplastic elastomer |
| CN102676195B (en) * | 2012-05-23 | 2014-04-02 | 徐国财 | Chemical modification method of coal pitch with unsaturated thermoplastic elastomer |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN102942172B (en) * | 2012-11-22 | 2014-08-20 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN104031669B (en) * | 2013-03-07 | 2016-08-10 | 神华集团有限责任公司 | A kind of electrode pitch and preparation method thereof |
| CN104031669A (en) * | 2013-03-07 | 2014-09-10 | 神华集团有限责任公司 | Electrode pitch and preparation method thereof |
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| CN103288070B (en) * | 2013-04-02 | 2015-08-19 | 大连理工大学 | Coal liquefaction residue heavy organic component is utilized to prepare the method for N doping porous charcoal |
| CN103326024A (en) * | 2013-06-14 | 2013-09-25 | 苏州诺信创新能源有限公司 | Preparation method of intermediate phase graphite for lithium-ion battery negative material |
| CN103614153A (en) * | 2013-11-29 | 2014-03-05 | 神华集团有限责任公司 | Preparation method of polycondensed asphalt, preparation method of needle coke and needle coke |
| CN103613089A (en) * | 2013-11-29 | 2014-03-05 | 神华集团有限责任公司 | Method of preparing mesocarbon microbeads by coal liquefaction residues and mesocarbon microbeads |
| CN103614153B (en) * | 2013-11-29 | 2015-06-24 | 神华集团有限责任公司 | Preparation method of polycondensed asphalt, preparation method of needle coke and needle coke |
| CN103613089B (en) * | 2013-11-29 | 2016-02-10 | 神华集团有限责任公司 | Coal liquefaction residue is utilized to prepare method and the MCMB of MCMB |
| CN105720233A (en) * | 2014-12-04 | 2016-06-29 | 神华集团有限责任公司 | Carbon material for lithium ion battery negative electrode and preparation method for carbon material, lithium ion battery negative electrode and lithium ion battery |
| CN105720233B (en) * | 2014-12-04 | 2020-05-22 | 神华集团有限责任公司 | Carbon material for lithium ion battery cathode, preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN105838409A (en) * | 2015-01-12 | 2016-08-10 | 神华集团有限责任公司 | Method for preparing mesophase pitch from residues of coal liquefaction and prepared mesophase pitch |
| CN105838408A (en) * | 2015-01-12 | 2016-08-10 | 神华集团有限责任公司 | Method for preparing mesophase pitch from residue derived from coal liquefaction and prepared mesophase pitch |
| CN105838409B (en) * | 2015-01-12 | 2019-03-15 | 神华集团有限责任公司 | The method of coal liquefaction residue mesophase pitch and mesophase pitch obtained |
| CN105838408B (en) * | 2015-01-12 | 2019-02-19 | 神华集团有限责任公司 | A kind of method of coal liquefaction residue mesophase pitch and mesophase pitch obtained |
| CN105905883A (en) * | 2016-04-15 | 2016-08-31 | 神华集团有限责任公司 | Mesocarbon microbead and preparation method thereof |
| CN106497591B (en) * | 2016-10-21 | 2019-05-07 | 湖南东映碳材料科技有限公司 | A kind of preparation method catalyzing and synthesizing mesophase pitch |
| CN106497591A (en) * | 2016-10-21 | 2017-03-15 | 湖南大学 | A kind of preparation method for catalyzing and synthesizing mesophase pitch |
| CN108258242A (en) * | 2016-12-28 | 2018-07-06 | 上海宝钢化工有限公司 | Preparation method of high-performance artificial graphite anode material precursor |
| CN108258242B (en) * | 2016-12-28 | 2020-11-10 | 宝武炭材料科技有限公司 | Preparation method of high-performance artificial graphite anode material precursor |
| CN106811235A (en) * | 2016-12-29 | 2017-06-09 | 中石化南京工程有限公司 | A kind of device and method of mink cell focus/residual oil/coal tar catalytic cracking polymerisation lighting |
| CN106753495A (en) * | 2016-12-29 | 2017-05-31 | 中石化南京工程有限公司 | A kind of method of high temperature coal-tar/residual oil production carbosphere and dipping agent bitumen |
| CN107021471A (en) * | 2017-05-31 | 2017-08-08 | 中国科学院山西煤炭化学研究所 | A kind of method that medium temperature coal pitch prepares MCMB |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| US11369941B2 (en) | 2017-10-26 | 2022-06-28 | Posco Chemical Co., Ltd. | Method for preparing porous carbon material by using coal tar generated in COG process |
| CN111263731B (en) * | 2017-10-26 | 2022-12-23 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| CN108485694A (en) * | 2018-04-11 | 2018-09-04 | 北京化工大学 | A method of carbonizatin method prepares high-quality mesophase pitch altogether |
| CN108611114A (en) * | 2018-05-31 | 2018-10-02 | 山西豪仑科化工有限公司 | A kind of method of coal liquifaction dregs of fat extraction |
| CN109082292A (en) * | 2018-09-04 | 2018-12-25 | 福建海峡能源集团股份有限公司 | A kind of technique for extracting pitch from putty slag |
| CN109504416A (en) * | 2018-12-04 | 2019-03-22 | 大同新成新材料股份有限公司 | A kind of production technology of coal-based needle coke |
| CN109504415A (en) * | 2018-12-04 | 2019-03-22 | 大同新成新材料股份有限公司 | A kind of production method of needle coke |
| CN113508169B (en) * | 2019-03-04 | 2024-09-13 | 杰富意钢铁株式会社 | Method for evaluating coal, method for producing mixed coal, and method for producing coke |
| CN113508169A (en) * | 2019-03-04 | 2021-10-15 | 杰富意钢铁株式会社 | Method for evaluating coal, method for producing coal blend, and method for producing coke |
| CN110357089A (en) * | 2019-06-24 | 2019-10-22 | 鞍钢股份有限公司 | Method for cleaning carbon microspheres by using N, N-dimethyl formamide |
| CN110499175A (en) * | 2019-09-04 | 2019-11-26 | 北京旭阳科技有限公司 | A method of super regular high-purity pitch coke is prepared by mid temperature pitch |
| CN111547715A (en) * | 2020-04-28 | 2020-08-18 | 鞍钢股份有限公司 | Method for improving yield of mesocarbon microbeads |
| CN113667506B (en) * | 2020-05-15 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method and preparation system of mesophase pitch |
| CN113667506A (en) * | 2020-05-15 | 2021-11-19 | 中国石油化工股份有限公司 | Preparation method and preparation system of mesophase pitch |
| CN114477126A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Mesocarbon microbeads and preparation method thereof |
| CN112642417A (en) * | 2020-12-10 | 2021-04-13 | 西安凯立新材料股份有限公司 | Preparation method and application of dehydrogenation catalyst carrier |
| CN112831334B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Preparation method of mesophase pitch and mesophase carbon microspheres |
| CN112831334A (en) * | 2021-01-13 | 2021-05-25 | 中国石油大学(华东) | Preparation method of mesophase pitch and mesophase carbon microspheres |
| CN113247878A (en) * | 2021-06-30 | 2021-08-13 | 北京化工大学 | Preparation method and application of asphalt-based carbon microspheres |
| CN115521802A (en) * | 2022-09-16 | 2022-12-27 | 北京化工大学 | Method for preparing mesophase pitch by catalysis of cocatalyst-Lewis acid system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102225755B (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102225755B (en) | Preparation method of mesophase carbon microspheres from coal liquefaction residues | |
| CN102399565B (en) | Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof | |
| CN101580729B (en) | Method for preparing mesophase asphalt by coal liquefaction residue | |
| CN103013566B (en) | A kind of technique utilizing coal-tar pitch to prepare needle-shape coke raw material | |
| CN102399566B (en) | Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction | |
| CN102491307B (en) | Method for preparing mesocarbon microbeads by copolycondensation | |
| CN105958072A (en) | Preparation method of natural flake graphite-based negative electrode material | |
| CN103614153B (en) | Preparation method of polycondensed asphalt, preparation method of needle coke and needle coke | |
| CN103613089B (en) | Coal liquefaction residue is utilized to prepare method and the MCMB of MCMB | |
| CN103833007A (en) | Preparation method of coal pitch-based mesocarbon microbeads | |
| CN107720721A (en) | MCMB and preparation method thereof | |
| WO2014051180A1 (en) | Method for reforming coal using palm residue | |
| CN1100093C (en) | Prepn. method of mesophase asphalt carbon microsphere | |
| JP4160095B2 (en) | Highly filling carbonaceous powder for electrode plates of non-aqueous electrolyte secondary batteries | |
| CN102942172B (en) | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material | |
| JP5530292B2 (en) | Manufacturing method of coke for steel making | |
| CN113604241B (en) | Method for preparing needle coke by medium-low temperature coal tar pitch composite extraction modification | |
| CN109082292B (en) | A kind of technique for extracting pitch from putty slag | |
| Guo et al. | Co-carbonization effect of asphaltine and heavy oil in mesophase development | |
| CN1308113A (en) | Copolycondensation preparation of intermediate phase carbon microsphere | |
| WO2014175121A1 (en) | Method for manufacturing ashless coal, and method for manufacturing carbon material | |
| CN103173025A (en) | Method for preparing road asphalt by direct coal liquefaction residue | |
| CN102633245A (en) | Control method of intermediate phase carbon microball D50 and device for producing intermediate phase carbon microball | |
| KR101359266B1 (en) | Method for Preparing of Coal Pitch | |
| CN111392707B (en) | Method for preparing mesocarbon microbeads by direct coal liquefaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130227 Termination date: 20140526 |