CN102041014A - Ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from coal direct liquefaction residue - Google Patents
Ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from coal direct liquefaction residue Download PDFInfo
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Abstract
The invention relates to an ionic liquid composite extracting agent for separating asphaltene, preasphaltene and/or heavy oil from coal direct liquefaction residue, and a method for the ionic liquid composite extracting agent to separate the asphaltene, the preasphaltene and/or the heavy oil from the coal direct liquefaction residue. The ionic liquid composite extracting agent comprises ionic liquid and organic solvent, wherein the ionic liquid comprises at least one kind of imidazole basic ion and at least one kind of organic and/or inorganic negative ion; and the organic solvent comprises at least one kind of alcohol, amine, ketone and/or pyridine solvent which is mutually soluble to the ionic liquid. The asphaltene, the preasphaltene and/or the heavy oil obtained through ionic liquid composite extracting agent is further separated to get the asphaltene and/or the preasphaltene, the asphaltene and/or the preasphaltene can be modified to prepare mesophase pitches and further produce a series of high-performance carbon fiber materials, thereby implementing utilization of the coal direct liquefaction residue with high additional value.
Description
Technical field
The present invention relates to a kind of being used for from the ionic liquid composite extractant of coal directly-liquefied residue separate bitumen alkene, preceding asphaltene and/or mink cell focus, and the method for utilizing this ionic liquid composite extractant separate bitumen alkene, preceding asphaltene and/or mink cell focus from coal directly-liquefied residue.
Background technology
DCL/Direct coal liquefaction technology is under high-temperature and high-pressure conditions, under catalyst action, by hydrogenation reaction, coal is converted into the advanced person and the clean technology of the coal of liquid fuel or industrial chemicals.By DCL/Direct coal liquefaction technology, can produce oil products such as gasoline, diesel oil, aviation kerosene, petroleum naphtha, also can extract benzene, toluene and dimethylbenzene (being referred to as BTX) simultaneously, and the raw materials for production of important alkene such as ethene, propylene.As the effective technology of production oil substitutes, DCL/Direct coal liquefaction technology is to solving China's oil shortage of resources, balance energy structure, ensureing that energy security and national economy sustainable and stable development have great strategic importance and realistic meaning.
In the DCL/Direct coal liquefaction technological process, except obtaining liquid product, also produce the solid residue that accounts for raw coal total amount 20-30%.Effectively utilize these liquefied residues, the resource utilization and the economy of DCL/Direct coal liquefaction technology had immeasurable influence.Coal directly-liquefied residue is a kind of high-carbon, high ash and doctor positive material, and unconverted organic matter, inorganic mineral and the catalyzer that adds have constituted the main body of coal directly-liquefied residue in the coal.For many years, all constantly exploring the method for utilizing coal directly-liquefied residue both at home and abroad, at present, utilizing the method for coal directly-liquefied residue mainly to comprise: with liquefied residue gasification preparation synthetic gas; Liquefied residue is carried out destructive distillation obtain mink cell focus, retortable oil and coke; With liquefied residue as road asphalt modifier; Liquefied residue is directly burnt as solid fuel; The preparation CNT (carbon nano-tube); Preparation mesophase pitch and then production carbon fibre material etc.
Usually, the coal directly-liquefied residue outward appearance is the solid of pitch shape, temperature is raised to that softening temperature about 190 ℃ is above just to flow, its ash oontent is about 20%, thermal value is more than 25MJ/kg, carry the energy material so it still is a fine, but because of it has some special components, the product that utilizes these particular components to develop or isolate high added value is coal directly-liquefied residue research and utilizes one of most important direction.
In recent years, separate bitumen alkene and preceding asphaltene from coal directly-liquefied residue, prepare mesophase pitch after the modification, and then production carbon fiber, it is the research focus that coal directly-liquefied residue utilizes, wherein adopt method of extraction separate bitumen alkene and preceding asphaltene from coal directly-liquefied residue, so selection of Extractant is most important.
US2008/0072476 discloses a kind of gelatin liquefaction fuel that is mixed with alcohol, gasoline or other fuel, wherein, gelatin liquefaction fuel is by carrying out hydrogenation distillation or obtain by DCL/Direct coal liquefaction is carried out solvent extraction to coal tar, the decanted oil that the extraction solvent that is adopted comprises aromatic series heavy oil, obtain through refining of petroleum or contain other oil just like the compound of naphthalene or tricyclic aromatic molecule.
US2008/0017549 discloses a kind of through extracting the method that is prepared synthetic asphalts by coal, and extraction solvent is selected from coal tar distillation liquid, petroleum distillation liquid, oil catalytic pyrolysis product, gasification pitch distillate, recycle hydrocarbons pyrolysis product and shale oil or tar sand distills the aromatic series oil product that is obtained.
CN101885976 discloses a kind of through extracting the method for extracting mink cell focus and mesophase pitch from coal directly-liquefied residue, and wherein, extraction agent is the liquefaction oil product that produces in the DCL/Direct coal liquefaction process; CN101580729A discloses a kind of asphaltene that utilizes in the organic solvent extraction coal liquefaction residue, and then the method for mesophase pitch is produced in modification, wherein the organic extraction solvent comprises N, N-N,N-DIMETHYLACETAMIDE, furfural, N, one or more in dinethylformamide, tetrahydrofuran (THF), N-N-methyl-2-2-pyrrolidone N-, dithiocarbonic anhydride, quinoline, the pyridine; CN1948148A discloses a kind of toluene and tetrahydrofuran (THF) of adopting and has extracted the method that asphaltene and preceding asphaltene and carbonization prepare CNT (carbon nano-tube) as extraction agent; CN1629257A discloses and adopted the asphaltene deposits thing that produces in pyridines and the quinoline ionic liquid dissolution with solvents Oil extraction, remove this asphaltene deposits thing, carry out the method for ionic liquid solvent reclamation again.
Above-mentioned document is introduced with for referencial use in full at this.
Above-mentioned traditional extraction agent is difficult to separate efficiently, apace asphaltene and preceding asphaltene in the coal directly-liquefied residue because of the extraction conditions harshness, cause asphaltene in the coal directly-liquefied residue and preceding asphaltene separation efficiency and disengaging time all to be difficult to satisfy practicality and industrialization demands, the traditional extraction solvent is volatile even poisonous simultaneously, and it is all unfriendly to operator and environment.Therefore need to seek and a kind ofly can separate asphaltene in the coal directly-liquefied residue and preceding asphaltene and environmentally friendly and make it to reach the novel extraction agent of practicality and industrial requirement efficiently, apace.
Ionic liquid is as a kind of novel " green solvent ", has the incomparable performance of conventional solvent, very strong as low, the liquid a wider range of fusing point, dissolving power, almost do not have that vapour pressure, volatility are little, thermostability and chemical stability better, can be recycled etc., obtained the extensive approval of countries in the world chemist, and obtained very important use in electrochemistry, catalysis with in separating, especially on the separated fiber element, obtained bigger progress.The mixture of attempting at present utilizing ionic liquid and organic solvent separates asphaltene in the coal directly-liquefied residue as composite extractant and the work of preceding asphaltene does not still have bibliographical information.
Based on above present Research, the inventor is through a large amount of tests and creative work, specific ion liquid and specific organic solvent are mixed with certain proportion, form composite extractant, be used for separating efficiently, apace the asphaltene and the preceding asphaltene of coal directly-liquefied residue, its beneficial effect is to improve separation efficiency greatly, effectively reduce extraction, isolating time and organic solvent consumption, avoid separately with an organic solvent and the secondary pollution that forms etc., therefore, it has broad application prospects.
Simultaneously, separate the asphaltene and/or the preceding asphaltene that obtain with ionic liquid composite extractant of the present invention and can prepare mesophase pitch, and then produce a series of high-performance carbon fibre materials, thereby realize the high value added utilization of coal directly-liquefied residue through modification.
Summary of the invention
The objective of the invention is in order to overcome the above-mentioned deficiency of utilizing coal directly-liquefied residue, utilize coal directly-liquefied residue with realizing high added value, more particularly, the objective of the invention is to utilize novel ionic liquid composite extractant by useful components such as asphaltene in the extracting and separating coal directly-liquefied residue and preceding asphaltenes, produce mesophase pitch for next step modification and supply raw materials.
According to an aspect of the present invention, provide a kind of being used for to comprise from the ionic liquid composite extractant of coal directly-liquefied residue separate bitumen alkene, preceding asphaltene and/or mink cell focus:
The organic solvent that 1-99 weight % ionic liquid and 99-1 weight % and described ionic liquid are dissolved each other,
Wherein, described ionic liquid comprises at least a imidazoles positively charged ion and at least a organic and/or inorganic anion; Described organic solvent comprises at least a alcohol, amine, ketone and/or pyridines solvent.
Preferably, above-mentioned ionic liquid composite extractant comprises the organic solvent that 20-80 weight % ionic liquid and 80-20 weight % and described ionic liquid are dissolved each other, and more preferably, comprises the organic solvent that 40-60 weight % ionic liquid and 60-40 weight % and described ionic liquid are dissolved each other.
In a preferred embodiment of the invention, in the above-mentioned ionic liquid composite extractant, described organic solvent is ethylene glycol, 1-Methyl-2-Pyrrolidone, ethanol, thanomin, trolamine, pyridine and/or their mixture; And described imidazoles positively charged ion is at least a ion that has the imidazoles of different side chain carbon numbers or contain glyoxaline structure; Described organic and/or inorganic anion is chlorion (Cl
-), bromide anion (Br
-), iodide ion (I
-), trifluoromethyl sulphamide ion (Tf
2N
-), tetrafluoroborate ion (BF
4 -), hexafluorophosphoricacid acid ions (PF
6 -), trifluoromethane sulfonic acid radical ion (CF
3SO
3 -), sulfate ion (SO
4 2-), carboxylic acid ion (RCOO
-), nitrate ion (NO
3 -) and fluoroform butyrate ion (CF
3CF
2CF
2CF
2SO
3 -) and/or their mixture.
In preferred embodiment of the present invention, described ionic liquid is chlorination 1-butyl-3-methylimidazole salt: [Bmim] Cl, chlorination 1-ethyl-3-methylimidazole salt: [Emim] Cl, 1-octyl group-3-Methylimidazole fluoroborate: [Omim] [BF
4], 1-ethyl-3-Methylimidazole acetate: [Emim] [OAC], 1-octyl group-2,3-methylimidazole fluoroborate: [Odmim] [BF
4], 1-hexyl-2,3-methylimidazole fluoroborate: [Hdmim] [BF
4] and/or their mixture.
Usually ionic liquid composite extractant consumption is not done special qualification, but consider from efficient and economy aspect, the consumption of described ionic liquid composite extractant is preferably: the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is about 0.5-3/10, and the weight ratio that is more preferably the described ionic liquid in described coal directly-liquefied residue and the described ionic liquid composite extractant is about 1/10.
In preferred embodiment of the present invention, described ionic liquid and water are immiscible under room temperature or low temperature, but are being higher than more than 60 ℃, then dissolve each other in the time of particularly more than 70 ℃, such ionic liquid for example is a 1-hexyl-2,3-methylimidazole fluoroborate: [Hdmim] [BF
4]; And can further extract again and be separated from each other through distillation, fractionation and/or solvent with the mixture that ionic liquid composite extractant of the present invention separates the asphaltene, preceding asphaltene and/or the mink cell focus that obtain.
According to another aspect of the present invention, provide a kind of method of utilizing above-mentioned ionic liquid composite extractant separate bitumen alkene, preceding asphaltene and/or mink cell focus from coal directly-liquefied residue, it may further comprise the steps in order:
Particle diameter is joined in the extraction container that contains described ionic liquid composite extractant less than the coal directly-liquefied residue of 3 weight % less than 1mm, water content, and wherein said ionic liquid composite extractant and coal directly-liquefied residue ratio are: the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is 0.5-3/10;
Under the extraction temperature of room temperature-150 ℃, stirring coal directly-liquefied residue the extraction container and solid-liquid mixtures 5-120 minute of described ionic liquid composite extractant continuously or intermittently, stop subsequently stirring and it being cooled to room temperature;
Subsequent filtration is removed wherein throw out and/or solid residue, and the liquid that obtains of suction filtration, randomly removes described organic solvent by distillation;
Be that described ionic liquid composite extractant volume 2-6 deionized water doubly carries out back extraction to wherein adding consumption again, thereby separate out solid;
Filtration obtains asphaltene, preceding asphaltene and/or mink cell focus solid product through the solid-liquid mixtures that back extraction obtains.
In the invention described above method, the particle diameter that joins the coal directly-liquefied residue in the extraction container that contains described ionic liquid composite extractant is preferably less than 150 microns; And the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is preferably 1/10.
In a preferred embodiment of the invention, extraction temperature is preferably more than 60 ℃, particularly more than 70 ℃; And more preferably stir coal directly-liquefied residue in the extraction container and solid-liquid mixtures 15-90 minute of described ionic liquid composite extractant continuously or intermittently; And preferably in the liquid that suction filtration obtains, add the deionized water be about 4 times of described ionic liquid composite extractant volumes.
One of the present invention more preferably in the embodiment, described method further comprises extracting through distillation, fractionation and/or solvent again described asphaltene, preceding asphaltene and/or mink cell focus solid product is further separated.
According to a further aspect of the invention, provide a kind of raw material that is used to prepare mesophase pitch and/or carbon fibre material, wherein separate the asphaltene and/or the preceding asphaltene that obtain and be used to prepare mesophase pitch and/or carbon fibre material according to aforesaid method.
Embodiment
Test by the Shenhua direct coal liquefaction residue that the continuous experimental installation of DCL/Direct coal liquefaction (0.1t/d BSU) to 100 kg/day of Chinese China Coal Research Institute produces, liquefied residue derives from high-temperature separator and discharges the bottoms material of material after underpressure distillation, finds that its true density is 1.43g/cm
3, point of inversion is 193 ℃ under the room temperature.Analyze through Soxhlet (SOHEX) extraction, the chemical constitution of above-mentioned coal directly-liquefied residue is as follows:
Table 1
(weight %) is composed as follows for the element of above-mentioned coal directly-liquefied residue:
Table 2
| C? | H? | O? | N? | S? | H/C? | O/C? |
| 84.08? | 6.40? | 4.97? | 1.46? | 3.07? | 0.91? | 0.04? |
By above-mentioned table 1 as can be known: soluble component in the Shenhua direct coal liquefaction residue (mink cell focus, asphaltene and preceding asphaltene) accounts for 50.58% of residue gross weight; And asphaltene and preceding asphaltene ingredients constitute residue gross weight 25.78%.
As can be known, asphaltene is the mixture of a large amount of differing moleculars from existing research, nearly 45 kinds more than of its compound structure unit, and molecular-weight average is 1387, obtains its average mark minor by ultimate analysis and molecular-weight average data computation to be: C
101H
90.6O
3.6N
2Its primary structure is to encircle to condense on aromatic hydrocarbon and the aromatic ring to have alkyl substituent more, partial hydrogenation is saturated for wherein a small amount of aromatic nucleus, the chain length of the substituted alkyl on the aromatic nucleus differs, 13 carbon atoms of average out to, compare with the mink cell focus component, methyl chains is more relatively. and a small amount of oxygen and nitrogen-atoms are in ring and go up the formation heterocycle, and have small amount of hydroxyl groups and ether. and the pyrolysis gas chromatography mass spectrum is found to have tetrahydrofuran polymer in the sample.Below be the average molecular structure model of asphaltene:
(weight %) is composed as follows for the element of the asphaltene in the above-mentioned coal directly-liquefied residue:
Table 3
| C? | H? | O? | N? | S? | H/C? | O/C? |
| 87.19? | 6.53? | 4.17? | 2.08? | 0.03? | 0.90? | 0.04? |
Equally, the mink cell focus component in the Shenhua direct coal liquefaction residue also is the mixture of a large amount of differing moleculars, nearly 34 kinds more than of its compound structure unit, and molecular-weight average is 339, average mark minor C
25H
310
0.2N
0.26, its primary structure is the aromatic hydrocarbon of 2-3 ring, wherein some fractional saturation become naphthenic hydrocarbon, have alkyl substituent on aromatic nucleus and the saturated rings, substituent chain length differs, an average out to 9-10 carbon. a small amount of oxygen and nitrogen-atoms are in ring and go up the formation heterocycle.Below be the average molecular structure model of mink cell focus:
The element of mink cell focus (weight %) is composed as follows in the above-mentioned coal directly-liquefied residue:
Table 4
| C? | H? | O? | N? | S? |
| 88.71? | 9.16? | 0.99? | 1.07? | 0.07? |
Above-mentioned partial data and molecular structure derive from reference (Gu Xiaohui, Shi Shidong, Zhou Ming; The molecular structure research of Shenhua direct coal liquefaction residue medium pitch olefinic constituent; The coal journal, 2006,31 (6): 785-789) with (Gu Xiaohui, Zhou Ming, Shi Shidong; The molecular structure of mink cell focus component research in the Shenhua direct coal liquefaction residue; The coal journal, 2006,31 (1): 76-80).Above-mentioned document is introduced with for referencial use in full at this.
Because soluble component comprises mink cell focus (HS) in the coal directly-liquefied residue, asphaltene (HI-BS), with preceding asphaltene (BI-THFS), therefore, with the isolated material of ionic liquid composite extractant of the present invention is mink cell focus (HS), the mixture of asphaltene (HI-BS) and preceding asphaltene (BI-THFS), mink cell focus (HS) wherein, asphaltene (HI-BS) and preceding asphaltene (BI-THFS) promptly are dissolved in the organic solvent of the present invention, also be dissolved in the ionic liquid of the present invention, when carrying out back extraction with deionized water, organic solvent and ionic liquid are dissolved in the deionized water, and be insoluble to the mink cell focus (HS) of deionized water, asphaltene (HI-BS) and preceding asphaltene (BI-THFS) are then separated out as solid, if organic solvent is insoluble to deionized water, then before back extraction, earlier organic solvent is removed, thereby realized mink cell focus (HS) by distilling, insolubles separates in asphaltene (HI-BS) and preceding asphaltene solvends such as (BI-THFS) and the coal directly-liquefied residue.
Ionic liquid of the present invention is to the solvend in the coal directly-liquefied residue, particularly asphaltene and preceding asphaltene and mink cell focus have very strong dissolving power, simultaneously it is liquid state in the temperature range of room temperature-150 ℃, and volatility is little, thermostability and chemical stability are good again, can be recycled, so, it is the novel dissolvent of ideal asphaltene and preceding asphaltene, but because its viscosity is higher, when it uses separately, the stirring resistance increases, thereby churning time can be forced to prolong, but when itself and the compound use of organic solvent of the present invention, not only can make its viscosity be reduced to greatly can be practical degree, but also produce synergistic effect, solubleness or effect of extracting strengthen greatly.
Ionic liquid composite extractant of the present invention comprises: the organic solvent that 1-99 weight % ionic liquid and 99-1 weight % and described ionic liquid are dissolved each other, and wherein, described ionic liquid comprises at least a imidazoles positively charged ion and at least a organic and/or inorganic anion; Described organic solvent comprises at least a alcohol, amine, ketone and/or pyridines solvent.
Usually, should not do further qualification to the ratio of ionic liquid composite extractant intermediate ion liquid of the present invention and organic solvent again.But go to consider that preferably, above-mentioned ionic liquid composite extractant comprises the organic solvent that 10-90 weight % ionic liquid and 90-10 weight % and described ionic liquid are dissolved each other from efficient and economy equilibrated angle; More preferably, comprise the organic solvent that 20-80 weight % ionic liquid and 80-20 weight % and described ionic liquid are dissolved each other; Particularly comprise the organic solvent that 40-60 weight % ionic liquid and 60-40 weight % and described ionic liquid are dissolved each other.
In ionic liquid composite extractant of the present invention, some ionic liquid and water are immiscible under room temperature or low temperature, but under slightly high temperature, then dissolve each other in the time of for example more than 60 ℃ or 70 ℃, such ionic liquid for example is a 1-hexyl-2,3-methylimidazole fluoroborate: [Hdmim] [BF
4].The ionic liquid composite extractant that is composited by above-mentioned ionic liquid and organic solvent has following beneficial technical effects: the asphaltene in extraction and/or back extraction coal directly-liquefied residue under the temperature of dissolving each other at above-mentioned ionic liquid and water, when preceding asphaltene and/or mink cell focus, in extraction, the optional distillation of organic solvent, after finishing with the back extraction process, when ionic liquid composite extractant of the present invention is cooled to room temperature or low temperature, ionic liquid and water, or the mixture of ionic liquid and water and organic solvent is not owing to dissolve each other AUTOMATIC ZONING, ionic liquid and water have so just been saved, or the separating step of the mixture of ionic liquid and water and organic solvent, become simpler thereby make back extraction process and ionic liquid or organic solvent recycle.
As an example, above-mentioned organic solvent for example is ethylene glycol, 1-Methyl-2-Pyrrolidone, ethanol, thanomin, trolamine, pyridine and/or their mixture; Above-mentioned imidazoles positively charged ion for example is at least a ion that has the imidazoles of different side chain carbon numbers or contain glyoxaline structure; Above-mentioned organic and/or inorganic anion for example is chlorion: Cl
-, bromide anion: Br
-, iodide ion: I
-, trifluoromethyl sulphamide ion: Tf
2N
-, tetrafluoroborate ion: BF
4 -, hexafluorophosphoricacid acid ions: PF
6 -, trifluoromethane sulfonic acid radical ion: CF
3SO
3 -, sulfate ion: SO
4 2-, carboxylic acid ion: RCOO
-, nitrate ion: NO
3 -, fluoroform butyrate ion: CF
3CF
2CF
2CF
2SO
3 -And/or their mixture.
As preferred examples, ionic liquid of the present invention for example is chlorination 1-butyl-3-methylimidazole salt: [Bmim] Cl, chlorination 1-ethyl-3-methylimidazole salt: [Emim] Cl, 1-octyl group-3-Methylimidazole fluoroborate: [Omim] [BF
4], 1-ethyl-3-Methylimidazole acetate: [Emim] [OAC], 1-octyl group-2,3-methylimidazole fluoroborate: [Odmim] [BF
4], 1-hexyl-2,3-methylimidazole fluoroborate: [Hdmim] [BF
4] and/or their mixture.
Usually, above-mentioned ionic liquid composite extractant consumption is not done special restriction, but consider from benefit and economy aspect, above-mentioned ionic liquid composite extractant consumption is preferably: the weight ratio of the ionic liquid in coal directly-liquefied residue and the ionic liquid composite extractant is 0.1-5/10, more preferably 0.5-3/10; Be preferably 0.8-2/10 especially; And most preferably be 1/10.
Because separating the material that obtains through ionic liquid composite extractant of the present invention is the solid mixt of asphaltene, preceding asphaltene and/or mink cell focus, want further from above-mentioned solid mixt, to isolate asphaltene and/or preceding asphaltene, need for example do processing such as distillation, fractionation and/or solvent extract again to above-mentioned solid mixt, thereby asphaltene and/or preceding asphaltene and mink cell focus are separated.Processes such as above-mentioned distillation, fractionation and/or solvent extract again are the conventional separating technologies of chemical field, for well known to those of ordinary skill in the art, in order to save space, are not described in detail at this.
Use ionic liquid composite extractant of the present invention to separate the asphaltene in the coal directly-liquefied residue, preceding asphaltene and/or mink cell focus in accordance with the following methods:
Particle diameter is joined in the extraction container that contains above-mentioned ionic liquid composite extractant less than the coal directly-liquefied residue of 3 weight % less than 1mm, water content, and wherein said ionic liquid composite extractant and coal directly-liquefied residue ratio are: the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant be 0.1-5/10, more preferably 0.5-3/10, be preferably 0.8-2/10 especially and most preferably be 1/10;
From room temperature-150 ℃, preferably more than 60 ℃, more preferably under the extraction temperature more than 70 ℃, stir coal directly-liquefied residue in the extraction container and solid-liquid mixtures 1-180 minute, preferred 5-120 minute, more preferably 15-90 minute of ionic liquid composite extractant continuously or intermittently, stop subsequently stirring and it is cooled to room temperature or below the room temperature;
Subsequent filtration is removed wherein throw out and/or solid residue, and the liquid that obtains of suction filtration, randomly removes described organic solvent by distillation;
Consumption is described ionic liquid composite extractant volume 1-10 times, preferred 2-6 times, more preferably 4 times deionized water carries out back extraction to wherein adding again, thereby separates out solid;
Filtration obtains asphaltene, preceding asphaltene and/or mink cell focus solid product through the solid-liquid mixtures that back extraction obtains.
In aforesaid method, the particle diameter that joins the coal directly-liquefied residue in the extraction container that contains described ionic liquid composite extractant preferably less than 800 microns, be more preferably less than 500 microns, especially preferably less than 300 microns most preferably less than 150 microns, usually, the particle diameter of coal directly-liquefied residue is more little, the surface-area that contacts with ionic liquid composite extractant of the present invention is just big more, the extraction time is just short more, and extraction efficiency is just good more.
In a preferred embodiment of the present invention, aforesaid method also further comprises through processes such as distillation, fractionation and/or solvent extract again described asphaltene, preceding asphaltene and/or the further separation steps of mink cell focus solid-phase mixture product, so separate resulting asphaltene in back and/or preceding asphaltene and can be used as starting material, be used to prepare mesophase pitch and/or carbon fibre material.
Specifically, in the process of extracting and separating, also can be crushed to certain particle diameter, dried coal directly-liquefied residue joins in the above-mentioned ionic liquid, adds certain amount of organic solvent then, as 1-Methyl-2-Pyrrolidone, ethanol or pyridine etc., make both form composite extractant of the present invention.The ratio that the consumption of organic solvent accounts for the extraction agent total mass is 1%-99%.Under pressure 0.1atm-50atm, in the 273K-473K temperature range, coal directly-liquefied residue is extracted.After liquid after extraction finished leaves standstill, ash content in the coal directly-liquefied residue and the insolubles such as catalyzer or the indissoluble thing that are used for gelatin liquefaction can precipitate or separate out, asphaltene, preceding asphaltene and/or mink cell focus be dissolved into the extraction agent formed by organic solvent and ionic liquid mutually in, add a certain amount of deionized water and/or distilled water back extraction to extraction agent in mutually after the filtering separation, the mixture of asphaltene, preceding asphaltene and/or mink cell focus is very fast separates out with the solid form, just can obtain the product that needs after filtering.If ionic liquid and water do not dissolve each other under room temperature or low temperature, but under higher extraction and/or back extraction temperature, dissolve each other, when temperature reduces, ionic liquid and water or with the mixture of water and organic solvent with AUTOMATIC ZONING, the two separates and is very easy to; If ionic liquid and water also dissolve each other under room temperature or low temperature, can remove organic solvent and water respectively by underpressure distillation after, resulting regeneration organic solvent and ionic liquid can be recycled.
One of innovative point of the present invention is specific ion liquid and specific organic solvent are mixed the formation composite extractant in certain proportion, make advantages such as the production cost that extracting and separating efficient improves greatly, the environment of extracting and separating is gentle, total more is low, extraction agent is easy to regeneration, processing unit is simple, be easy to realize industrialization.
It is to be noted: in technical solution of the present invention, " coal " in " coal directly-liquefied residue " refers to coal, carbon containing biomass, refinery coke, carbon solid waste and/or the carbonaceous mud of all kinds, and the carbonaceous slag etc.
Further describe the present invention with detailed one exemplary embodiment below, but these embodiment do not constitute any limitation of the invention.
Embodiment
Embodiment 1
The about 0.5004g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 5.0285g[Bmim be housed] in the Erlenmeyer flask of Cl and 20ml (20.52g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 90 ℃, after the about 5min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains carries out back extraction to wherein adding about 4 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains the 0.2552g solid product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 51%.Underpressure distillation obtains before the 0.1291g asphaltene respectively and asphaltene more afterwards, and the 0.1241g mink cell focus.
Embodiment 2
The about 0.5027g particle diameter of weighing is about 178 microns (80 order) coal directly-liquefied residues, join 5.0175g[Emim be housed] in the Erlenmeyer flask of Cl and 20ml (20.52g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 80 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 5 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains carries out back extraction to wherein adding about 2 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.3334g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 66.32%.
Embodiment 3
The about 0.5045g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, joins 5.0005g[Hdmim is housed] [BF
4] and the Erlenmeyer flask of 20ml (20.52g) 1-Methyl-2-Pyrrolidone composite extractant in, under the room temperature, after the about 15min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop to stir, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains, the solution that suction filtration is obtained is heated to 70 ℃, treat temperature-stable after, carry out back extraction to wherein adding about 6 times of deionized waters to ionic liquid composite extractant volume, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2876g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 57%.Liquid phase cools after filtering is during to room temperature, to be separated into ionic liquid and water and ORGANIC SOLVENT MIXTURES two-phase automatically, the two is very easy to separate because of layering, and water can further separate by distillation with ORGANIC SOLVENT MIXTURES simultaneously, and ionic liquid and organic solvent after the separation can be recycled.
Embodiment 4
The about 0.5102g particle diameter of weighing is about 150 millimeters (100 order) coal directly-liquefied residues, joins 5.1135g[Odmim is housed] [BF
4] and the Erlenmeyer flask of 20ml (20.52g) 1-Methyl-2-Pyrrolidone composite extractant in, under the room temperature, after the about 15min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop to stir, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains adds about 4 times of deionized waters to ionic liquid composite extractant volume and carries out back extraction, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2255g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 44.2%.
Embodiment 5
The about 0.5087g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, joins 5.0655g[Omim is housed] [BF
4] and the Erlenmeyer flask of 20ml (15.8g) ethanol composite extractant in, heating treats that temperature-stable is in the time of 60 ℃, after the about 20min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains, distill out ethanol after, add about 4 times of deionized waters and carry out back extraction to ionic liquid composite extractant volume, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.1384g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 27.2%.
Embodiment 6
The about 0.5078g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 5.0465g[Emim be housed] in the Erlenmeyer flask of [OAC] and 20ml (15.8g) ethanol composite extractant, under the room temperature, after the about 15min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop to stir, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains, distill out ethanol after, add about 4 times of deionized waters and carry out back extraction to ionic liquid composite extractant volume, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.0863g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 17%.
Embodiment 7
The about 0.5024g particle diameter of weighing is about 800 microns coal directly-liquefied residues, join 5.0367g[Emim be housed] in the Erlenmeyer flask of Cl and 10ml (11.247g) trolamine composite extractant, under the room temperature, after the about 15min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop to stir, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains adds about 4 times of deionized waters to ionic liquid composite extractant volume and carries out back extraction, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.0987g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 19%.
Embodiment 8
The about 0.5084g particle diameter of weighing is about 450 microns (40 order) coal directly-liquefied residues, join 5.0679g[Bmim be housed] in the Erlenmeyer flask of Cl and 20ml (19.6g) pyridine composite extractant, heating, treat that temperature-stable is in the time of 70 ℃, after the about 45min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains carries out back extraction to wherein adding about 4 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains the 0.1471g solid product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 29%.
Embodiment 9
The about 0.2507g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 4.6178g[Bmim be housed] in the Erlenmeyer flask of Cl and 0.5ml (0.513g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 120 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 5 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains carries out back extraction to wherein adding about 6 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.1094g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 43.6%.
Embodiment 10
The about 0.6627g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 2.2815g[Bmim be housed] in the Erlenmeyer flask of Cl and 20ml (20.52g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 100 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 10 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains carries out back extraction to wherein adding about 4 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2314g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 34.9%.
Embodiment 11
The about 0.5247g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 5.129g[Bmim be housed] in the Erlenmeyer flask of Cl and 1.25ml (1.2825g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 110 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 10 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains carries out back extraction to wherein adding about 6 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2414g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 46%.
Embodiment 12
The about 0.5038g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join 5.0186g[Bmim be housed] in the Erlenmeyer flask of Cl and 7.5ml (7.6854g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 90 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 8 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains carries out back extraction to wherein adding about 5 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2739g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 54.36%.
Embodiment 13
The about 0.5049g particle diameter of weighing is about 100 microns (150 order) coal directly-liquefied residues, join 5.375g[Bmim be housed] in the Erlenmeyer flask of Cl and 3.5ml (3.59g) 1-Methyl-2-Pyrrolidone composite extractant, heating, treat that temperature-stable is in the time of 100 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 10 minutes rhythm stir about 120min in 1 minute, stop heated and stirred, and be cooled to room temperature, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains carries out back extraction to wherein adding about 6 times of deionized waters to ionic liquid composite extractant volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2458g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 48.7%.
The comparative example
The comparative example 1
The about 0.5086g particle diameter of weighing is about 178 microns (80 order) coal directly-liquefied residues, join 5.0258g[Bmim be housed] in the Erlenmeyer flask of Cl ionic liquid extraction agent, heating, treat that temperature-stable is in the time of 90 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 5 minutes rhythm stir about 180min in 1 minute, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains carries out back extraction to wherein adding about 8 times of deionized waters to the extraction agent volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.0814g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 16%.
The comparative example 2
The about 0.5079g particle diameter of weighing is about 178 microns (80 order) coal directly-liquefied residues, join in the Erlenmeyer flask that 20ml (20.52g) 1-Methyl-2-Pyrrolidone organic solvent extract is housed, heating, treat that temperature-stable is in the time of 90 ℃, to the Erlenmeyer flask continuously stirring of solid-liquid mixtures be housed or with after stirring 5 minutes rhythm stir about 180min in 1 minute, stop heated and stirred, and be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains carries out back extraction to wherein adding about 4 times of deionized waters to above-mentioned organic solvent volume subsequently, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.2286g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 45%.
The comparative example 3
The about 0.5068g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, joins 5.0175g[Hdmim is housed] [BF
4] in the Erlenmeyer flask of ionic liquid extraction agent, under the room temperature, after the about 75min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop to stir, with solution strainer insolubles residual or that be precipitated out is filtered out.The solution that suction filtration obtains, the solution that suction filtration is obtained is heated to 70 ℃ subsequently, treat temperature-stable after, carry out back extraction to wherein adding about 8 times of deionized waters to the extraction agent volume, can see obviously that at this moment solid separates out.Solid-liquid mixtures after the back extraction filters with solution strainer once more, obtains 0.0856g solid phase product, is the mixture of asphaltene, preceding asphaltene and mink cell focus, and productive rate is about 16.9%.Liquid phase cools after filtering will be separated into ionic liquid and water two-phase during to room temperature automatically, the two be very easy to separate because of layering and water sepn after ionic liquid can be recycled.
The comparative example 4
The about 0.5089g particle diameter of weighing is about 150 microns (100 order) coal directly-liquefied residues, join in the Erlenmeyer flask that 20ml (15.8g) ethanol organic solvent extract is housed, heating, treat that temperature-stable is in the time of 60 ℃, after the about 45min of Erlenmeyer flask continuously stirring of solid-liquid mixtures is housed, stop heated and stirred, be cooled to room temperature, insolubles residual or that be precipitated out is filtered out with solution strainer.The solution that suction filtration obtains, distill out ethanol after, obtain 0.0559g solid phase product, be the mixture of asphaltene, preceding asphaltene and mink cell focus, productive rate is about 11%.
From the foregoing description and comparative example's data as can be seen: ionic liquid of the present invention and organic solvent composite extractant have very satisfied extracting power, compare as extraction agent with independent use ionic liquid or organic solvent, has good synergistic function, simultaneously, extraction conditions is also relatively gentleer, its extraction time shortens greatly, and organic solvent and deionized water consumption significantly reduce.This is extremely useful for the application of industrially scalable.
Although represented and described plurality of embodiments of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize under the situation that does not break away from principle of the present invention and essence, can carry out any accommodation and improvement to these embodiments, and protection domain of the present invention is determined by appended claim and equivalent thereof.
Claims (21)
1. one kind is used for comprising from the ionic liquid composite extractant of coal directly-liquefied residue separate bitumen alkene, preceding asphaltene and/or mink cell focus:
The organic solvent that 1-99 weight % ionic liquid and 99-1 weight % and described ionic liquid are dissolved each other,
Wherein, described ionic liquid comprises at least a imidazoles positively charged ion and at least a organic and/or inorganic anion; Described organic solvent comprises at least a alcohol, amine, ketone and/or pyridines solvent.
2. ionic liquid composite extractant according to claim 1, it comprises the organic solvent that 20-80 weight % ionic liquid and 80-20 weight % and described ionic liquid are dissolved each other.
3. ionic liquid composite extractant according to claim 2, it comprises the organic solvent that 40-60 weight % ionic liquid and 60-40 weight % and described ionic liquid are dissolved each other.
4. ionic liquid composite extractant according to claim 1, wherein said organic solvent are ethylene glycol, 1-Methyl-2-Pyrrolidone, ethanol, thanomin, trolamine, pyridine and/or their mixture.
5. ionic liquid composite extractant according to claim 1, wherein said imidazoles positively charged ion are at least a ions that has the imidazoles of different side chain carbon numbers or contain glyoxaline structure.
6. ionic liquid composite extractant according to claim 1, wherein said organic and/or inorganic anion is a chlorion: Cl
-, bromide anion: Br
-, iodide ion: I
-, trifluoromethyl sulphamide ion: Tf
2N
-, tetrafluoroborate ion: BF
4 -, hexafluorophosphoricacid acid ions: PF
6 -, trifluoromethane sulfonic acid radical ion: CF
3SO
3 -, sulfate ion: SO
4 2-, carboxylic acid ion: RCOO
-, nitrate ion: NO
3 -, fluoroform butyrate ion: CF
3CF
2CF
2CF
2SO
3 -And/or their mixture.
7. ionic liquid composite extractant according to claim 1, wherein said ionic liquid are chlorination 1-butyl-3-methylimidazole salt: [Bmim] Cl, chlorination 1-ethyl-3-methylimidazole salt: [Emim] Cl, 1-octyl group-3-Methylimidazole fluoroborate: [Omim] [BF
4], 1-ethyl-3-Methylimidazole acetate: [Emim] [OAC], 1-octyl group-2,3-methylimidazole fluoroborate: [Odmim] [BF
4], 1-hexyl-2,3-methylimidazole fluoroborate: [Hdmim] [BF
4] and/or their mixture.
8. ionic liquid composite extractant according to claim 1, the consumption of wherein said ionic liquid composite extractant is: the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is 0.5-3/10.
9. ionic liquid composite extractant according to claim 8, the weight ratio of the described ionic liquid in wherein said coal directly-liquefied residue and the described ionic liquid composite extractant is 1/10.
10. ionic liquid composite extractant according to claim 1, the temperature of dissolving each other of wherein said ionic liquid and water is more than 60 ℃.
11. ionic liquid composite extractant according to claim 10, the temperature of dissolving each other of wherein said ionic liquid and water further is more than 70 ℃.
12. ionic liquid composite extractant according to claim 1, wherein said asphaltene, preceding asphaltene and/or mink cell focus further extract through distillation, fractionation and/or solvent again and are separated from each other.
13. one kind with the method according to one of any ionic liquid composite extractant separate bitumen alkene, preceding asphaltene and/or mink cell focus from coal directly-liquefied residue of aforementioned claim 1-12, it may further comprise the steps in order:
Particle diameter is joined in the extraction container that contains described ionic liquid composite extractant less than the coal directly-liquefied residue of 3 weight % less than 1mm, water content, and wherein said ionic liquid composite extractant and coal directly-liquefied residue ratio are: the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is 0.5-3/10;
Under the extraction temperature of room temperature-150 ℃, stirring coal directly-liquefied residue the extraction container and solid-liquid mixtures 5-120 minute of described ionic liquid composite extractant continuously or intermittently, stop subsequently stirring and it being cooled to room temperature;
Subsequent filtration is removed wherein throw out and/or solid residue, and the liquid that obtains of suction filtration, randomly removes described organic solvent by distillation;
Be that described ionic liquid composite extractant volume 2-6 deionized water doubly carries out back extraction to wherein adding consumption again, thereby separate out solid;
Filtration obtains asphaltene, preceding asphaltene and/or mink cell focus solid product through the solid-liquid mixtures that back extraction obtains.
14. method according to claim 13, the particle diameter that wherein joins the coal directly-liquefied residue in the extraction container that contains described ionic liquid composite extractant is less than 150 microns.
15. method according to claim 13, wherein the weight ratio of the described ionic liquid in coal directly-liquefied residue and the described ionic liquid composite extractant is 1/10.
16. method according to claim 13, wherein extraction temperature is more than 60 ℃.
17. method according to claim 13, wherein extraction temperature further is more than 70 ℃.
18. method according to claim 13 wherein stirs coal directly-liquefied residue in the extraction container and mixture 15-90 minute of described ionic liquid composite extractant continuously or intermittently.
19. method according to claim 13 wherein is incorporated as the deionized water of 4 times of described ionic liquid composite extractant volumes in the liquid that suction filtration obtains.
20. method according to claim 13 further comprises extracting through distillation, fractionation and/or solvent again described asphaltene, preceding asphaltene and/or mink cell focus solid product is further separated.
21. method according to claim 20 is separated the asphaltene and/or the preceding asphaltene that obtain and is used to prepare mesophase pitch and/or carbon fibre material.
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Cited By (7)
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| CN102391185A (en) * | 2011-09-05 | 2012-03-28 | 天津大学 | Ionic liquid for assisting oil-sand separation and separation method |
| CN107286971A (en) * | 2017-07-07 | 2017-10-24 | 辽宁大学 | A kind of method that pitch in separation oil-sand is floated by pitch |
| CN107312560A (en) * | 2017-06-29 | 2017-11-03 | 安徽和轩岩沥青科技有限公司 | A kind of dehydrating processing method of kir |
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| US20190316225A1 (en) * | 2018-04-17 | 2019-10-17 | Energy, United States Department Of | Extraction of rare earth elements and carbon rich solids from coal feedstock using ionic liquids |
| CN111841580A (en) * | 2020-08-06 | 2020-10-30 | 太原理工大学 | Hydrodesulfurization catalyst based on coal liquefaction oil residue raffinate and preparation method thereof |
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| CN101260314A (en) * | 2008-05-04 | 2008-09-10 | 中国科学院过程工程研究所 | Oil oxidation-extraction desulfurization technique based on ionic liquid composite solvent |
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| CN102391185B (en) * | 2011-09-05 | 2014-04-16 | 天津大学 | Ionic liquid for assisting oil-sand separation and separation method |
| CN107312560A (en) * | 2017-06-29 | 2017-11-03 | 安徽和轩岩沥青科技有限公司 | A kind of dehydrating processing method of kir |
| CN107286971A (en) * | 2017-07-07 | 2017-10-24 | 辽宁大学 | A kind of method that pitch in separation oil-sand is floated by pitch |
| CN107286971B (en) * | 2017-07-07 | 2019-03-15 | 辽宁大学 | A method of pitch in separation oil-sand is floated by pitch |
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| CN113457204B (en) * | 2021-06-02 | 2022-05-31 | 中国神华煤制油化工有限公司 | Method for extracting coal directly to liquefy oil residue by using coking crude benzene |
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