CN103059894A - Method for extraction and separation of carbon-containing coal residues based on ionic liquid - Google Patents
Method for extraction and separation of carbon-containing coal residues based on ionic liquid Download PDFInfo
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- CN103059894A CN103059894A CN 201110320513 CN201110320513A CN103059894A CN 103059894 A CN103059894 A CN 103059894A CN 201110320513 CN201110320513 CN 201110320513 CN 201110320513 A CN201110320513 A CN 201110320513A CN 103059894 A CN103059894 A CN 103059894A
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- ionic liquid
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Abstract
The invention provides a technology for separating asphaltene materials from carbon-containing solid residues generated in a coal processing process based on an ionic liquid extracting agent. The technology employs pyridine and ammonium ionic liquid as the extracting agent to separate the asphaltene materials from carbon-containing residues through two steps of extraction and reverse extraction at a certain temperature and pressure, and provides high-quality raw materials for modifying and preparing mesophase asphalt and further producing high performance carbon materials. The ionic liquid used by the method is easy to synthesize, is cheap, has low viscosity and is easy to regenerate. Compared with a convention extraction separation method by using an organic solvent, the method can obviously increase separation selectivity of the asphaltene materials in the residues, has relatively low H/C ratio and sulfur content of the extract, and almost contains no soluble substances such as quinoline. The technology has the advantages of environment protection, energy conservation, simple equipment, convenient operations, low investment, simplified production process, easily realizable automatic control, etc.
Description
Technical field:
The present invention relates to a kind of take ionic liquid as extraction agent, the method for separating the carbonaceous solids residue medium pitch alkene class material that the coal machining process produces.
Background technology:
The characteristics of China energy resource are rich coal resources, and oil, Sweet natural gas are relatively deficient, and these characteristics have determined that the energy structure of China is take coal as main body, and coal is difficult to change within the long duration as the general layout of China's main energy sources.Greatly develop the trend that the Coal Chemical Industry industry is China's energy development, relate to a plurality of fields such as heavy chemicals of coking, gasification, indirect liquefaction, direct liquefaction and the coal of coal.Efficient, clean coal resources that take full advantage of how reduce that oil is in short supply, and the coordinated development that realizes the energy, economy, environment is the current urgent and strategic task of tool of China.
The main products of the techniques such as coal directly or indirectly liquefies, coking is fuel gas, oil fuel, inevitably produces simultaneously a certain amount of solid residue, and for example, the residue that the DCL/Direct coal liquefaction process produces accounts for 30% of raw coal total amount.Further effectively utilize these residues, the efficient clean utilization of coal resources and the economy of Coal dressing technique are had immeasurable impact.Mainly comprise mink cell focus, asphaltene class material, unreacted coal and mineral substance etc. in the carbonaceous residues that the coal machining process produces, wherein asphaltene class material mainly is comprised of the condensed aromatics of many rings, have that aromaticity is high, carbon content is high, easy polymerization or the characteristics such as crosslinked, being important aromatic carbon resource, is the high quality raw material of preparation high performance carbon cellulosic material.At present, the mode of utilizing of coal carbonaceous residues has direct burning, coking liquefaction, gasification hydrogen-producing etc., wherein take burning as main, does not have realization to the high value added utilization of residue medium pitch alkene class material.
Prepare mesophase pitch after utilizing the isolated asphaltene class of coal carbonaceous residues substance modification, and then production high added value carbon materials such as carbon fiber, needle coke etc., be a study hotspot of coal residue high value added utilization.Reported the liquefied coal coil pitch that utilizes in the organic solvent extraction coal residue in the Chinese patent (publication number CN101580729A), and then the technology of mesophase pitch is produced in modification; The heavy liquefaction oil that utilizes in the liquefaction oil product extraction coal liquefaction residue that produces in the gelatin liquefaction process and the method for bitumen have been reported in the Chinese patent (publication number CN101885976A).Reported employing toluene and tetrahydrofuran (THF) extraction asphaltene and preasphaltene in the Chinese patent (publication number CN1948148A), and carbonization prepares the technology of CNT (carbon nano-tube).Reported employing pyridines and quinoline ion liquid solvent dissolving removing Oil extraction studies on asphaltene settling in the Chinese patent (publication number CN1629257A), the method for remove bituminous matter, regenerating.
Ionic liquid is as a kind of novel " green solvent ", has the incomparable characteristic of conventional organic solvents, as steam force down, not volatile, fusing point is low, have very strong dissolving power, preferably thermostability and chemical stability, wider liquid scope, can be recycled etc., be widely used in electrochemistry, catalysis, material synthetic with the chemical field such as separate, especially obtained larger progress at the separated fiber element.Attempt at present utilizing pure ionic liquid almost not have as the bibliographical information of phase in the middle of the asphaltene class material in the extraction agent separation coal carbonaceous residues and the further preparation.The asphaltene, preasphaltene and/or the mink cell focus that adopt in the ionic liquid composite extractant separation coal directly-liquefied residue have been reported in the Chinese patent (publication number CN102041014A), wherein used ionic liquid positively charged ion is imidazoles, and the residue of processing is coal directly-liquefied residue; And the extraction agent that the present invention uses be pure ionic liquid and positively charged ion is pyridines and ammonium class, and the coal carbonaceous residues of processing comprise coal directly/coke tar refuse in the indirect liquefaction residue, coal tar process and coal tar distillation residue etc., both protect content different.
Based on above present Research, the present invention adopts two steps of extraction and back-extraction take ionic liquid as extraction agent, separates efficiently, fast the asphaltene class material in the coal carbonaceous residues.It is advantageous that used ionic liquid can one-step synthesis, inexpensive, viscosity is low, be easy to regeneration, effectively shortens the extracting and separating time, the secondary pollution that forms when avoiding using the organic solvent extraction and separation can improve the extracting and separating selectivity simultaneously greatly.Mesophase pitch by the preparation of asphaltene class substance modification is the presoma of preparation high performance carbon cellulosic material, thereby the present invention has broad application prospects.
Summary of the invention:
The objective of the invention is the low value-added present situation of utilizing for the carbonaceous residues of present coal machining process generation, carry out the high value added utilization of coal residue.Developed a kind ofly take ionic liquid as extraction agent, separated the effective ways of coal carbonaceous residues medium pitch alkene class material, thereby supplied raw materials for preparation high quality carbon cellulosic material.
The ionic liquid that uses among the present invention is comprised of pyridines, ammonium cationoid and carboxylic-acid, sulfuric acid dialkyl esters negatively charged ion.Wherein pyridines, ammonium cationoid are a kind of in the pyridine that contains hydrogen or different side chain carbon numbers, the ammonium ion, and negatively charged ion is formate ion (Of
-), acetate ion (OAc
-), propionate ion (OP
-), benzoate anion ion (Ba
-), methyl-sulfate ion (DMS
-) and ethyl sulfate ion (DES
-).The structural formula of above ionic liquid can be exemplified below:
Triethylammonium formate ionic liquid ([TEtA] [Of]) 3-picoline acetate ionic liquid ([MPy] [OAc])
Triethylamine propionic salt ionic liquid ([TEtA] [OP]) 3-picoline benzoate ionic liquid ([MPy] [Ba])
1-ethyl-3-picoline ethyl sulfate salt ion liquid ([EMPy] [DES])
In the process of extracting and separating, the coal carbonaceous residues that is crushed to certain particle diameter is joined in the dry above-mentioned ionic liquid.20 ℃～120 ℃ of pressure 1atm～50atm, temperature, carry out extraction experiments in the scope of time 5min～90min.Behind the filtering separation residue insolubles, add a certain amount of distilled water at ionic liquid in mutually, asphaltene class material is very fast separates out with solid form, after filtration, obtain the target extract after dry.Extract H/C atomic ratio is between 0.60～0.98, and sulphur content is the high quality raw material of phase in the middle of the preparation less than 0.5%.And the ionic liquid recycling capable of circulation that ionic liquid aqueous solution obtains after underpressure distillation or electrodialysis dewater.
Innovative point of the present invention is take inexpensive, low viscous pure ionic liquid as extraction agent, through two steps of extraction and back-extraction, separate the asphaltene class material in the coal residue, have that the production cost that the extracting and separating selectivity improves greatly, the environment of extracting and separating is gentleer, total is low, ionic liquid is easy to recycling, processing unit is simple, be easy to realize the advantages such as industrialization.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, and in the scope of described aim, change is included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Weighing is the 1.0217g coal directly-liquefied residue approximately, joins 10.0166g[TEtA is housed] in the beaker of [Of] ionic liquid.Heating, treat temperature-stable in the time of 30 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 15min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 10 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain after drying the 0.1079g solid phase prod, be asphaltene class mixture, productive rate is about 10.60%, H/C and is about 0.81, S content approximately 0.20% can be used as the raw material of preparation mesophase pitch.
Embodiment 2
Weighing is 1.0029g coal tar distillation residue approximately, joins 8.0097g[TEtA is housed] in the beaker of [OP] ionic liquid.Heating, treat temperature-stable in the time of 40 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 30min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 12 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain after drying the 0.5793g solid phase prod, be asphaltene class mixture, productive rate is about 57.76%, H/C and is about 0.96, S content is about 0.288%, can be used as the raw material of preparation mesophase pitch.
Embodiment 3
Weighing is the 1.0061g coal directly-liquefied residue approximately, joins 10.0575g[MPy is housed] in the beaker of [OAc] ionic liquid.Heating, treat temperature-stable in the time of 30 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 30min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 10 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain after drying the 0.3087g solid phase prod, be asphaltene class mixture, productive rate is about 30.68%, H/C and is about 0.76, S content is about 0.10%, can be used as the raw material of preparation mesophase pitch.
Embodiment 4
Weighing is 1.0014g coal tar distillation residue approximately, joins 8.0665g[EMPy is housed] in the beaker of [DES] ionic liquid.Heating, treat temperature-stable in the time of 60 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 40min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 10 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain after drying the 0.4877g solid phase prod, be asphaltene class mixture, productive rate is about 48.71%, H/C and is about 0.91, S content is about 0.49%, can be used as the raw material of preparation mesophase pitch.
Embodiment 5
Weighing is the 1.0031g coal directly-liquefied residue approximately, joins 6.0764g[TEtA is housed] in the beaker of [OP] ionic liquid.Heating, treat temperature-stable in the time of 30 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 30min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 8 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain the 0.2443g solid phase prod after the drying, be asphaltene class mixture, productive rate is about 24.35%, H/C and is about 0.87, S content is about 0.09%, can be used as the raw material of the middle pitch of preparation.
Embodiment 6
Weighing is 1.4162g coal tar distillation residue approximately, joins 16.9971g[MPy is housed] in the beaker of [Ba] ionic liquid.Heating, treat temperature-stable in the time of 40 ℃, place on the magnetic force heating stirrer continuously stirring approximately behind the 50min in the beaker that mixed solution is housed, stopped heating stirs, and with solution strainer insolubles is filtered out.In the mixing solutions that suction filtration obtains, add approximately 10 times to the deionized water of ionic liquid volume, obviously there is solid to separate out and layering, again filter with solution strainer and obtain solid matter, obtain after drying the 0.9983g solid phase prod, be asphaltene class mixture, productive rate is about 70.49%, H/C and is about 0.93, S content is about 0.35%, can be used as the raw material of preparation mesophase pitch.
Claims (6)
1. method based on the extracting and separating coal carbonaceous residues medium pitch alkene class material of ionic liquid is characterized in that take pyridine or ammonium class ionic liquid as extraction agent, under certain temperature and pressure, and the asphaltene class material in the extracting and separating coal carbonaceous residues.
2. method according to claim 1, coal carbonaceous residues comprise coke tar refuse in coal directly-liquefied residue, ICL for Indirect Coal Liquefaction residue, the coal tar process and coal tar distillation residue etc.
3. method according to claim 1, the ionic liquid that adopts is comprised of pyridines positively charged ion (1), ammonium cationoid (2) and carboxylic-acid negatively charged ion, sulfuric acid dialkyl esters negatively charged ion, have following general structure: A+B-, wherein A+ has general structure as follows:
R in the formula
1, R
2, R
3, R
4Meet following rule: (a) R
1For H or contain the hydrocarbyl substituent of 1-10 carbon atom; (b) R
2, R
3, R
4It is the hydrocarbyl substituent that contains 1-10 carbon atom; Described B
-Be following negatively charged ion: formate ion (Of
-), acetate ion (OAc
-), propionate ion (OP
-), benzoate anion ion (Ba
-), methyl-sulfate ion (DMS
-) and ethyl sulfate ion (DES
-).
4. method according to claim 1, wherein the service temperature of ion liquid abstraction coal carbonaceous residues medium pitch alkene class material is controlled between 20 ℃～120 ℃; Working pressure is between 1atm～50atm; The mass ratio of residue and ionic liquid is between 1: 2～1: 15; Extraction time is between 5min～90min; The volume ratio of reverse-extraction agent water and ionic liquid is between 6: 1～20: 1.
5. method according to claim 1, wherein the mode of extracting and separating coal carbonaceous residues medium pitch alkene class material is that residue is crushed between 50～200 orders, after adding a certain amount of ionic liquid, mode by continuously stirring, promote asphaltene class substance dissolves in ionic liquid, filter insolubles, filtrate is the asphaltene class material of dissolving and the mixture of ionic liquid.
6. method according to claim 5 is wherein filtered the filtrate behind the insolubles, adds distilled water and carries out back extraction, and the solid insoluble of separating out filters, drying is asphaltene class material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110320513 CN103059894A (en) | 2011-10-20 | 2011-10-20 | Method for extraction and separation of carbon-containing coal residues based on ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110320513 CN103059894A (en) | 2011-10-20 | 2011-10-20 | Method for extraction and separation of carbon-containing coal residues based on ionic liquid |
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| Publication Number | Publication Date |
|---|---|
| CN103059894A true CN103059894A (en) | 2013-04-24 |
Family
ID=48102801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110320513 Withdrawn CN103059894A (en) | 2011-10-20 | 2011-10-20 | Method for extraction and separation of carbon-containing coal residues based on ionic liquid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015077120A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing mercury from a coal tar product |
| WO2015076974A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing ash and heavy hydrocarbons from coal tar |
| WO2015077047A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing a product from coal tar |
| CN105419837A (en) * | 2015-11-09 | 2016-03-23 | 太原理工大学 | Carbon-bearing coal residue extraction separation method |
| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
| CN112812800A (en) * | 2020-12-23 | 2021-05-18 | 山东科技大学 | Method for extracting and separating alkaline nitride from coal tar by using proton type ionic liquid |
| CN113604241A (en) * | 2021-08-26 | 2021-11-05 | 西北大学 | Method for preparing needle coke by medium-low temperature coal tar pitch composite extraction modification |
| CN116332806A (en) * | 2022-12-29 | 2023-06-27 | 如皋市万利化工有限责任公司 | Preparation method and application of octyl diethyl dimethyl sulfate |
-
2011
- 2011-10-20 CN CN 201110320513 patent/CN103059894A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015077120A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing mercury from a coal tar product |
| WO2015076974A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing ash and heavy hydrocarbons from coal tar |
| WO2015077047A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for removing a product from coal tar |
| US9222034B2 (en) | 2013-11-19 | 2015-12-29 | Uop Llc | Process for removing a product from coal tar |
| CN105722954A (en) * | 2013-11-19 | 2016-06-29 | 环球油品公司 | Process for removing mercury from coal tar product |
| CN105419837A (en) * | 2015-11-09 | 2016-03-23 | 太原理工大学 | Carbon-bearing coal residue extraction separation method |
| CN105419837B (en) * | 2015-11-09 | 2017-11-28 | 太原理工大学 | A kind of coal carbonaceous residues extraction separating method |
| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
| CN112812800A (en) * | 2020-12-23 | 2021-05-18 | 山东科技大学 | Method for extracting and separating alkaline nitride from coal tar by using proton type ionic liquid |
| CN113604241A (en) * | 2021-08-26 | 2021-11-05 | 西北大学 | Method for preparing needle coke by medium-low temperature coal tar pitch composite extraction modification |
| CN116332806A (en) * | 2022-12-29 | 2023-06-27 | 如皋市万利化工有限责任公司 | Preparation method and application of octyl diethyl dimethyl sulfate |
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Application publication date: 20130424 |