CN102225755B - Preparation method of mesophase carbon microspheres from coal liquefaction residues - Google Patents
Preparation method of mesophase carbon microspheres from coal liquefaction residues Download PDFInfo
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- CN102225755B CN102225755B CN 201110137897 CN201110137897A CN102225755B CN 102225755 B CN102225755 B CN 102225755B CN 201110137897 CN201110137897 CN 201110137897 CN 201110137897 A CN201110137897 A CN 201110137897A CN 102225755 B CN102225755 B CN 102225755B
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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 the 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 Study on Coal coking 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 approximately 350～550 ℃ of middle temperature, inert atmosphere, the molecular weight that forms gradually through series of chemical such as pyrolysis, dehydrogenation and polycondensations is large, higher, the thermodynamically stable condensation condensed-nuclei aromatics of planeness, 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 that the pitch class organic compound of liquid state is to the middle mesomorphic state of solid carbon transit time, therefore be called again Carbonaceous mesophase or carbonaceous liquid crystal.
The preparation of MCMB is take liquid phase charing theory as instructing.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 anisotropic degree, mesophasespherule has experienced generation, the process of disintegration and carbon structure formation of melting also, grow up.Theoretical according to the liquid phase charing, 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 (such as pyridine insoluble PI amount, quinoline insolubles QI amount), additional substance (such 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 significant impact.The 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 the 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 mesophase ball or the middle also mesophase pitch of body that melts mutually, 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 technique is simple, facility investment is few and reaction is easy to the 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 lower material asphalt of inert atmosphere (such 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 soluble mesophase pitch about 300 ℃ is pulverized and is dissolved in the silicone oil with softening temperature, and heated and stirred becomes milk sap, and then cooling, centrifugation are also cleaned with benzene, just obtain MCMB after the drying.Suspension method is that soluble mesophase pitch is dissolved in the solvent, makes it form suspension under tensio-active agent, and then strong stirring is made the mesophase pitch bead under the certain temperature, reheat, cool off, filter analyse, 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 technique is simple, cost is lower.Indirect method, the technique 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, in order to 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 technique.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, processes under certain pressure, and again through Overheating Treatment, classification obtains later on MCMB of appropriate particle size etc.
In addition on the one hand, the characteristics of China's primary energy source resource are " many coals, few oil, scarce Sweet natural gases ".China be transformed into from oil exportiog countries be provided with, Imported gas big country.Along with the increase of Global Oil produced quantity and the minimizing of reserves, the breach of oil supply is increasing, thereby take full advantage of abundant coal resources, the deep exploitation technology of greatly developing product of coal is the risk that diversification reduces oil supply, 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 liquid effluent gasifying device together.Surplus materials after the parting liquid carburetion is called liquefied residue, and it is the material of a kind of high-carbon, high ash and high-sulfur, and output generally reaches about 30% of feed coal.So no matter consider from economy or environmental angle, all be the important component part of coal liquefaction craft exploitation to the utilization research of residue.For example: Chinese patent 200510047800.X discloses take coal liquefaction residue as raw material and has prepared carbon nano-material; Chinese patent 200610012547.9 discloses take coal liquefaction residue as the raw material production road asphalt modifier; Patent 200910086158.4 is take coal liquefaction residue as raw material, direct production body mesophase pitch, simultaneously, this patent also hinted coal liquefaction residue produce in the middle of the potentiality of phase product.
Usually the MCMB distribution of sizes that generates after direct heat is processed is wider, and yield is lower.Grown up the thus improvement technology of some preparation MCMB, Chinese patent CN1278513A openly adopts the itrated compound that adds iron, nickel, cobalt in the 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 to add anion surfactant and washing oil etc. and produce preferably mesophase ball of narrow size distribution and sphericity, this method has been avoided the use of a large amount of polar solvents such as pyridine, quinoline etc., is conducive to reduce cost; US Patent No. 4381990 adopts two step method of cooling to come the homogenizing crystallisation process, so that the mesophase ball that generates has narrow size distribution.The disclosed technical scheme of these patents is all being carried out improvement to a certain degree aspect the raising MCMB quality, but neither one 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, provide a kind of take coal liquefaction residue cheaply as raw material, technique 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 biodiversity content≤3%, to wherein adding in mass ratio extraction agent in 1: 3～1: 8, 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: add the chemical assistant of refined asphaltic bitumen quality 0.01～5% and 0.1～6% nucleation accelerating agent in the refined asphaltic bitumen that obtains to step a, 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 refined asphaltic bitumen quality.
Further, the consumption of described chemical assistant is 0.05～2.4% of refined asphaltic bitumen quality.
Further, the consumption of described nucleation accelerating agent is 1.5～3% of 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 again ganoid ball nature 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 raw material, wherein reactive large 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, meeting is so 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, the 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, although 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.Adopt the crosslinking reaction of chemical assistant between should control group dividing, also will promote the polycondensation between the phenyl ring simultaneously.Like this, whole reaction system is unlikely to viscosity too high and affect the distribution of bead particle diameter in generating the process of mesophase ball.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 on the content of quinoline insolubles with and size obvious impact is arranged, centrifugal rotational speed is lower than in the situation of some numerical value (this experiment whizzer is 4800r/min), and the QI content that obtains is higher and particle diameter is larger.High QI content can reduce the chemical property of MCMB, and that larger QI particle diameter can cause in the nucleation promoter action of QI in heat polymerization process is suppressed.So we are by the centrifugal pitch that at first obtains low QI content, and then the interpolation nucleation accelerating agent comes the effect of primary quinoline insolubles in the replacing asphalt.Nucleation accelerating agent can be 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 simultaneously whole system viscosity.
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.
For so that stirring rake is adopted in the system homogenization usually in heat treatment process.Wherein optimum stirring velocity is according to the difference of stirring rake design.If the system viscosity is larger, also can adopt higher rotating 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, again by suitable solvent wash, separate isotropic pitch and MCMB.The selection of cleaning solvent can be washing oil, middle oil, and carbolineum, perhaps organic solvent, such 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, usually contain 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 namely contains in the pitch so that the carbon microspheres surface free energy that generates is lower, thus in the forming process of MCMB, cause to short grained adsorptive power a little less than.
Compared with prior art, coal liquefaction residue of the present invention prepares the beneficial effect that the method for MCMB has: the present invention is gelatin liquefaction waste residue recycling cheaply, technique 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 carbon 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 carbon 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 extraction agent in mass ratio wherein: coal liquefaction residue be 1: 3～4 add in toluene, dimethylbenzene, the dimethyl sulfoxide (DMSO) a kind of, two or more, stirring 20min extracts, again centrifugation and remove insolubles under rotating speed 4800～7000r/min, 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 ℃;
Add the nucleation accelerating agent of refined asphaltic bitumen quality 2% and 0.7% chemical assistant in b, the refined asphaltic bitumen that obtains to step a.Be heated to the above temperature of softening temperature, then mix chemical assistant and nucleation accelerating agent.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, 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.
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 extraction agent in mass ratio wherein: 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 ℃.
Add the chemical assistant of refined asphaltic bitumen quality 1.3% and 1% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.Be heated to the above temperature of softening temperature, then mix chemical assistant and nucleation accelerating agent.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, 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 extraction agent in mass ratio wherein: 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 simultaneously two kinds) in tetrahydrofuran (THF)s, the N,N-DIMETHYLACETAMIDE, stir 30～40min and extract, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃.
Add the chemical assistant of refined asphaltic bitumen quality 1.8% and 1.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, 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 extraction agent in mass ratio wherein: 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 simultaneously two kinds) in dimethyl formamides and the dithiocarbonic anhydride, stir 50～60min and extract, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃.
Add the chemical assistant of refined asphaltic bitumen quality 1.3% and 1.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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), 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 extraction agent in mass ratio wherein: 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 simultaneously two kinds) in dimethyl formamides and the dithiocarbonic anhydride, stir 50～60min and extract, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃.
Add the chemical assistant of refined asphaltic bitumen quality 1.2% and 1.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, and chemical assistant comprises boron trifluoride/ether of accounting 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%.
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 extraction agent in mass ratio wherein: 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 simultaneously two kinds) in dimethyl sulfoxide (DMSO) and the N-Methyl pyrrolidone, stir 30～40min and extract, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃.
Add the chemical assistant of refined asphaltic bitumen quality 2.4% and 1.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, 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 respectively Fig. 1 and Fig. 2.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 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 extraction agent in mass ratio wherein: 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 ℃;
Add the chemical assistant of refined asphaltic bitumen quality 0.7% and 1.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, 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%.
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 extraction agent in mass ratio wherein: coal liquefaction residue is 1: 7～8 to add dimethyl sulfoxide (DMSO), stir 30～40min and extract, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃;
Add the chemical assistant of refined asphaltic bitumen quality 4% and 0.5% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, 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 extraction agent in mass ratio wherein: 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, again centrifugation and remove insolubles under rotating speed 4800～7000r/min.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 ℃;
Add the chemical assistant of refined asphaltic bitumen quality 0.05% and 4% nucleation accelerating agent in b, the refined asphaltic bitumen that obtains to step a.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, 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 does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (4)
1. a coal liquefaction residue prepares the method for MCMB, it is characterized in that comprising following preparation process:
1.1, preparation refined asphaltic bitumen: at first coal liquefaction residue is dried to biodiversity content≤3%, to wherein in mass ratio 1:3～1:8 add extraction agent, stir under 20～60min normal temperature and extract, separate by centrifugation again and remove insolubles, the gained extraction liquid is 200～300 ℃ of temperature, reduction vaporization under pressure≤0.2atm, obtain quinoline insolubles content and be 0.1～1% refined asphaltic bitumen, described extraction agent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, dimethyl formamide, in the dithiocarbonic anhydride one or more, described centrifugation adopts whizzer to separate, and the rotating speed of whizzer is 4800～7000r/min;
1.2, preparation mesophase ball: add in the refined asphaltic bitumen that obtains to step 1.1 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, reaction pressure is 0.5～2MPa, carry out thermal polycondensation reaction 3～10h under mixing speed 200～300r/min, make mesophase ball, described chemical assistant comprises aluminum chloride, pyridine alkane boron, resol, polystyrene, polyoxymethylene, iron, nickel, the muriate of cobalt, itrated compound or oxide compound, para benzoquinone, HEXACHLOROBUTADIENE, in boron trifluoride/ether complex one or more, consumption are 0.05～4% of refined asphaltic bitumen quality; Described nucleation accelerating agent comprises one or more in thin mica powder, nano level coke powder, nanometer grade silica, nano zircite, the nano-calcium carbonate, and consumption is 0.5～4% of refined asphaltic bitumen quality;
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, and the consumption that it is characterized in that described chemical assistant is 0.05～2.4% of refined asphaltic bitumen quality.
3. coal liquefaction residue according to claim 1 prepares the method for MCMB, and the consumption that it is characterized in that described nucleation accelerating agent is 1.5～3% of refined asphaltic bitumen quality.
4. 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.
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