CN102335522A - Method for grading utilization of coal - Google Patents
Method for grading utilization of coal Download PDFInfo
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- CN102335522A CN102335522A CN2011102630859A CN201110263085A CN102335522A CN 102335522 A CN102335522 A CN 102335522A CN 2011102630859 A CN2011102630859 A CN 2011102630859A CN 201110263085 A CN201110263085 A CN 201110263085A CN 102335522 A CN102335522 A CN 102335522A
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Abstract
The invention discloses a method for realizing grading utilization of coal by extracting the coal through mixing of supercritical carbon dioxide and an organic solvent. A method for extracting the solvent to separate a low molecular compound from a main body structure in the coal is an important method for clean and high-efficiency utilization of the coal. In the current general method of extracting by using a mixed solvent of CS2 and organic solvents (such as NMP (N-methyl-2-pyrrolidone) or DMF (Dimethyfumarate) and the like), toxic CS2 which is difficult in sequent separation is adopted, thus the wide application of the method is greatly limited. According to the method disclosed by the invention, non-toxic and harmless recyclable supercritical carbon dioxide is adopted to replace the CS2 and is simply separated from the organic solvent; the process is environment-friendly; the utilization efficiency of the coal can be effectively improved; and the grading utilization of the coal can be better realized.
Description
Technical field
The invention belongs to coal clean utilization field, be specifically related to the extraction of coal.
Background technology
Separating low molecular compound and agent structure in the coal through solvent-extracted method is a kind of important means for the utilization of clean and effective more for the research of the chemical constitution of coal and for coal itself.In numerous extracting process, carbon disulfide and organic solvent (like NMP or DMF etc.) carry out in the extraction research that isopyknic extraction that mixes is widely used in coal.Yet the method has following 2 deficiencies, the first, and carbon disulfide itself is a kind of noxious material, can cause certain injury to the health of human body in the experimentation, and the smell is awful easy firing again, has increased the danger of operation; The second,, solvent, solute, numerously changed separation process when separating because the existence of carbon disulfide has increased follow-up separating step.More than 2 amplifications that limited this method jointly use.Supercritical carbon dioxide is a kind of extractant of nontoxic, clean and effective, because its special nature in critical point place makes it very convenient with separating of solute, need not other separation equipment in addition.
Summary of the invention
The object of the invention promptly hopes to replace carbon disulfide and organic solvent (like NMP or DMF etc.) hybrid extraction coal with supercritical carbon dioxide.
The specific embodiment
Do further to detail below in conjunction with specific embodiment, the present invention is further described, but the present invention is not limited to following examples.
Embodiment
Getting the coal dust of certain mass pours in the high-pressure installation; In high-pressure installation, add the organic solvent such as the DMF of 1/2 volume, the flange screw of screwing on is positioned over the cooling of lowering the temperature in the mixture of ice and water with autoclave; Treat to open when the kettle temperature is reduced to below 5 ℃ steel cylinder pressure-reducing valve and autoclave inlet valve; Feed the carbon dioxide of certain hour, under this temperature and steel cylinder pressure (5MPa), partial CO 2 will existing with liquid form in the still; The length of duration of ventilation is looked concrete operating temperature, pressure and is decided, and the general relationship of duration of ventilation and temperature, pressure is obtained by the pre-stage test experience.Ventilation is closed the porch valve after finishing, and takes out autoclave, puts into body of heater after wiping away dried surface moisture; Open heater switch, heating kettle to preset temperature (this temperature need be higher than 31 ℃ of the critical-temperatures of supercritical carbon dioxide) is along with the rising of kettle temperature, pressure; The liquid phase carbon dioxide undergoes phase transition and gradually becomes gas phase in the still; The band temperature is higher than 31 ℃, and when pressure was higher than 7.1MPa, the carbon dioxide in the still existed with overcritical form; And under the effect of paddle with still in organic solvent be mixed into one mutually, and begin coal is extracted.
Extraction is closed paddle and heating power supply after accomplishing, and autoclave is taken out place water vat to cool off; Treat that temperature, pressure reduces to below the critical point; This moment, the carbon dioxide in the still became gas again, was divided into up and down two mutually with organic solvent, and solute is dissolved in the organic solvent.Open the autoclave outlet valve this moment; Emit carbon dioxide, pour out organic solvent and the surplus coal of collection at the bottom of the still, surplus coal repeatedly cleans with ethanol; Till cleaning fluid is colourless; Then put into baking oven oven dry, the surplus coal of weighing acquisition solid extract, extract uses decompression distillation to remove organic solvent, and concentrate passes through acetone solution with gas chromatograph-mass spectrometer (GC-MS) analytical extraction thing component.
Shown in Figure 1 is ScCO under 45 ℃, 7.4MPa and the 14.8MPa
2/ DMF and CS
2Relation in/DMF system extraction yield and the mixed solvent between the shared volume of DMF.
Visible by figure, pure ScCO during the single solvent extraction
2No matter high pressure still be under the low pressure value of extraction yield be 0, the extraction yield of pure DMF is 5.8%, that therefore plays the solvent extraction effect mainly comes from DMF but not ScCO
2, after both mixed, originally extraction yield rose along with the increase of the shared volume of DMF, and has reached maximum in 1: 1 place, just reduced with the increase of DMF volume ratio subsequently.Near by 1: 1 extraction yield is visible greater than the extraction yield of pure DMF, ScCO
2Existence to having promoted extraction, its curve shape and CS
2/ DMF system is quite similar, therefore can think same CS
2The same, ScCO
2And " synergistic effect " also taken place, i.e. ScCO between DMF
2In system, also played mediation and spread, reduced the effect of resistance to mass tranfer, and reached best proportioning at 1: 1 place.
Also can see the influence of pressure among the figure for extraction yield.Under uniform temp, the raising of pressure helps the carrying out that extract.According to the shooting flow volume property, pressure increases makes shooting flow solvent volume density increase, and fluid properties is drawn close to liquid, thus and produced better mixing between DMF.Yet the maximum amplification of extraction yield had only 13% after pressure improved 50% in this test, visible ScCO
2Be not the main influence of extraction process, thus also side light its secondary status in mixing.
Also can see ScCO among the figure in addition
2The effect of extracting of/DMF system all is lower than CS
2/ DMF, this can explain from thermodynamics, dynamics two aspects.From the thermodynamics angle, the height of extraction yield is relevant with the solubility parameter size of solvent with coal, and solubility parameter is approaching more, and extraction yield is high more.C content is lower than 80% bituminous coal solubility parameter δ c at 11.5～15.0 (cal.cm-3) between 0.5, CS
2The δ c of/DMF (1: 1) is about 11.1, and ScCO
2The δ c of/DMF (1: 1) is then about 9.6, so its effect of extracting is not as CS
2/ DMF; From the dynamics angle, the mass transfer diffusion process of solvent and extract affects extraction rate to a great extent, and actual extraction process more receives the influence of kinetic factor.Therefore extraction yield is low also possibly make ScCO owing to the reason that stirs in the still
2Fail to mix fully, thereby make ScCO with DMF
2Reducing the effect of diffusional resistance fails well to bring into play.
Through extract being used GCMS analyze, there is following product in the time of 45 ℃ under two kinds of pressure in the extract respectively:
Table 145 ℃, 7.4MPa, ScCO
21: 1 extract of/DMF is formed and content
It is thus clear that, in extract, have compounds such as phthalic acid fat, little molecule alkane, and these materials important chemical material just, therefore, mix can coal to be extracted after forming mixed solvent through the dizzy organic solvent of supercritical carbon dioxide.
Claims (8)
1. the extracting process of a novel coal is characterized in that using supercritical carbon dioxide and organic solvent as mixed solvent, and coal is extracted, and realizes the coal grading utilization.
2. the extracting process of coal as claimed in claim 1 is characterized in that employed coal is brown coal and other coal.
3. the extracting process of novel coal as claimed in claim 1 is characterized in that employed organic solvent is dimethyl formamide (DMF) or N-methyl pyrrolidone (NMP) or acetone.
4. the extracting process of novel coal as claimed in claim 1, the scope that it is characterized in that variations in temperature is at 45 ℃～150 ℃.
5. the extracting process of novel coal as claimed in claim 1, the excursion that it is characterized in that pressure is at 7.4MPa～30MPa.
6. the extracting process of novel coal as claimed in claim 1 is characterized in that the excursion of supercritical carbon dioxide shared volume fraction in mixed solvent is: 1-100%.
7. the extracting process of coal as claimed in claim 1 is characterised in that, the coal after the extraction repeatedly cleans with ethanol or acetone, and till cleaning fluid was colourless, oven dry then obtained the solid phase extraction coal.
8. the extracting process of coal as claimed in claim 1 is characterised in that, extract uses decompression distillation to remove organic solvent, and concentrate obtains extract through acetone or oxolane or n-hexane dissolution.
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| CN 201110263085 CN102335522B (en) | 2011-09-07 | 2011-09-07 | Method for grading utilization of coal |
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| CN 201110263085 CN102335522B (en) | 2011-09-07 | 2011-09-07 | Method for grading utilization of coal |
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| CN102335522B CN102335522B (en) | 2013-10-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101725A (en) * | 2018-03-10 | 2018-06-01 | 湖南科技大学 | A kind of method that low-order coal prepares chemicals |
| CN110835570A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction |
| CN110835569A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Method for removing organic sulfur in coal by using supercritical fluid hydrogenation reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2516218Y (en) * | 2001-12-18 | 2002-10-16 | 王有素 | Coal supercritical CO2 continuous extraction reaction device |
| CN101323793A (en) * | 2008-08-01 | 2008-12-17 | 中国科学技术大学 | Method for quality improving of biomass cracked oil by using supercritical carbon dioxide |
| CN101936861A (en) * | 2010-07-30 | 2011-01-05 | 中国矿业大学 | Test method of supercritical carbon dioxide content in coal |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2516218Y (en) * | 2001-12-18 | 2002-10-16 | 王有素 | Coal supercritical CO2 continuous extraction reaction device |
| CN101323793A (en) * | 2008-08-01 | 2008-12-17 | 中国科学技术大学 | Method for quality improving of biomass cracked oil by using supercritical carbon dioxide |
| CN101936861A (en) * | 2010-07-30 | 2011-01-05 | 中国矿业大学 | Test method of supercritical carbon dioxide content in coal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101725A (en) * | 2018-03-10 | 2018-06-01 | 湖南科技大学 | A kind of method that low-order coal prepares chemicals |
| CN110835570A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Test method for removing organic sulfur from coal by using swelling reaction to assist mass transfer effect of supercritical fluid extraction |
| CN110835569A (en) * | 2019-11-21 | 2020-02-25 | 山西焦煤集团有限责任公司 | Method for removing organic sulfur in coal by using supercritical fluid hydrogenation reaction |
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| CN102335522B (en) | 2013-10-02 |
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