CN103421567A - Pure coal and production method thereof - Google Patents
Pure coal and production method thereof Download PDFInfo
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- CN103421567A CN103421567A CN2013100102104A CN201310010210A CN103421567A CN 103421567 A CN103421567 A CN 103421567A CN 2013100102104 A CN2013100102104 A CN 2013100102104A CN 201310010210 A CN201310010210 A CN 201310010210A CN 103421567 A CN103421567 A CN 103421567A
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Abstract
The invention provides a method for producing pure coal, which comprises the step of soaking feed coal with an aqueous solution of hydrochloric acid/sulfuric acid, and an aqueous solution of hydrofluoric acid in sequence to remove ash in the feed coal. The ash content of the pure coal produced according to the method is equal to or lower than 0.8 percent or even lower; the calorific value of the pure coal is equal to or higher than 7500 kilocalorie per kilogram; the water content of the pure coal is equal to or lower than 10 percent; the pure coal is thin particles or powder. The pure coal can be used as fuel directly, while the combustion gas generated during the combustion of the pure coal can meet national smoke and dust emission standards without the treatment of dust removing equipment; the pure coal can be used in areas with high environment protection requirements.
Description
Technical field
The invention belongs to the fuel making field, particularly, the present invention relates to a kind of pure coal and production method thereof.
Background technology
Coal is most important primary energy source, accounts at present more than 60% of whole world primary energy source.The output of coal of China has reached more than 30 hundred million tons at present.The main application of coal is as fuel, but is different from other fuel, as oil, can all burn, and coal contains higher ash, thereby its combustion processes can be brought more serious environmental pollution.For this reason, invented and applied the equipment and process of multiple dedusting depositing dust, and, in the situation that coal ash part is heavy or association coal gangue ratio is higher, also adopted the method for coal washing to remove part of coal spoil and other impurity, thereby ature of coal raising, ash are reduced.Yet, adopt this type of physics or mechanical means can not remove the inherent ash in coal.Therefore, the flue dust produced during coal combustion must take measures to process could qualified discharge.Just, due to this, for protection of the environment, the many cities of China and regional regulation can not directly be burnt coal, but use oil firing, burning gas etc. instead.But the scarcity of hydrocarbon resources makes other fuel source price high, especially in the city and the area that do not have gas distributing system to cover, as can not be directly burnt coal, fuel cost is high, and then makes the production cost of industrial or agricultural and the Third Industry high, is unfavorable for economical and social development.
Therefore, this area, in the urgent need to a kind of inherent ash of removing in coal, makes its purer effective ways at present, so that this energy of coal can be used widely, can not bring environmental pollution simultaneously.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of novel method of producing pure coal, the coal that adopts the method to make is hardly containing ash (or ash is extremely low), but after burning, flue gas can be without dust removal installation with regard to qualified discharge.
Particularly, the invention provides following technical scheme:
On the one hand, the invention provides a kind of method of producing pure coal, the method comprises and adopts respectively hydrochloric acid or aqueous sulfuric acid, hydrofluoric acid aqueous solution to soak successively feed coal to remove the step of ash wherein.
The method specifically comprises the following steps:
(1) feed coal is ground into to particle or powder, then with hydrochloric acid or aqueous sulfuric acid, carries out immersion treatment;
(2) remove in step (1) after processing the soak solution formed, use the hydrofluoric acid aqueous solution immersion treatment after washing treated coal with water; And
(3) process the rear soak solution formed in removal step (2), wash treated coal extremely neutral with adjusting PH with base with water, then remove washings.
Wherein, the ash content of coal in the feed coal in step (1)≤8 % by weight, preferably≤5 % by weight; Preferably, total sulphur content in feed coal≤0.5 % by weight, volatile content >=25 % by weight.
Preferably, feed coal is ground into to particle or the powder below particle diameter 3mm, then carries out acid treatment; And the concentration of described hydrochloric acid or aqueous sulfuric acid is preferably 10-20 volume %, or be the hydrochloric acid of 4-7N concentration, the add-on of described hydrochloric acid and/or aqueous sulfuric acid is enough to remove the Al in ash
2O
3, Fe
2O
3, CaO, MgO; Preferably immersion treatment 3 hours or more than; Further preferably, twice of immersion treatment or more than.Oxide compound in " removal " as herein described ash is to instigate oxide compound and acid-respons in the ash composition to dissolve.
In addition, in step (2), the concentration of hydrofluoric acid aqueous solution is 10-20 volume %, or is the 4-7N concentration unit, and the add-on of described hydrofluoric acid aqueous solution is enough to remove the SiO in ash
2Preferably immersion treatment 6 hours or more than; Further preferably, twice of immersion treatment or more than.
And the alkali in step (3) is selected from Na
2CO
3, NaHCO
3Or NaOH.
On the other hand, the present invention also provides the pure coal of producing according to aforesaid method.
It is below detailed description of the present invention.
As everyone knows, in the middle of coal, aphlogistic ash chief component is: aluminum oxide (Al
2O
3), silicon-dioxide (SiO
2), ferric oxide (FeO), magnesium oxide (MgO), calcium oxide (CaO), calcium carbonate (CaCO
3) etc., they or Individual existence, or exist with the form of mineral salts, wherein except removing part of coal spoil, low grade coal by the method for physics or machinery, the inherent ash in the middle of coal can't be removed by general method.
Therefore, in the method for the invention, at first selecting coal ash part low fat coal of trying one's best is feed coal, such as regional ash such as originating in Xinjiang, Inner Mongol, Shanxi, Shanxi, is only 3.5% fat coal, and generally coal ash part≤8% gets final product.Certainly, consider the application of the finished product, when selecting feed coal, also should select the coal of low-sulfur, high-volatile as far as possible, as full sulphur should≤0.5%(is more low better), its fugitive constituent should be more high better, as >=35% etc.Available feed coal for example, originates from the coal in In A Certain Place of Xinjiang district, and ature of coal is: ash approximately 3.5%, fugitive constituent approximately 38%, full sulphur approximately 0.18%; Originate from the coal in somewhere, Shaanxi, ature of coal is: ash approximately 5.0%, fugitive constituent approximately 37%, full sulphur approximately 0.22%; Originate from the coal in somewhere, Inner Mongol, ature of coal is: ash approximately 3.9%, fugitive constituent approximately 35%, full sulphur approximately 0.21%.
Be after various ash form after analyzing the full composition of ash of coal, select targetedly the hydrochloric acid that soaks use or aqueous sulfuric acid etc. as the chemical processing agent of immersion treatment for the first time.As a rule, application hydrochloric acid; If in ash, CaO content is very low, as≤1%, available hydrochloric acid or sulfuric acid.This processing process is as follows: first the coal of selecting is broken into to 3mm following particle and powder, put into again acidproof pond or miscellaneous equipment, soak this kind of coal with the hydrochloric acid suitable by the theory weighing or aqueous sulfuric acid, liquid level should cover coal fully, soak time is not less than 3 hours (time is longer, and ash is dissolved must be more).After immersion, by the method for suction filtration, remove soak solution.Now the main component of soak solution comprises aluminum chloride, a small amount of calcium chloride, iron(ic) chloride etc., after concentrating, can use as water purification agent.Tested and regulated according to coal, the ash difference that becomes to grade, can add again hydrochloric acid (or sulfuric acid) aqueous solution soaking one to secondary, after analysis is found in coal ash part almost all to be dissolved by the ash of hydrochloric acid or sulfuric acid dissolution, suction filtration goes out soak solution again, and now soak solution can reclaim for soaking for the first time.After removing soak solution, soak again once (for washing the acid solution of coal) with clear water, and suction filtration falls soak solution.
Afterwards, according to the amount of the silicon-dioxide in the ash residuum, by theory, add hydrofluoric acid aqueous solution to soak, in this process, the silicon dioxde reaction in hydrofluoric acid and ash generates silicofluoric acid.Identical with abovementioned steps, in the time of also should soaking with test by the soak time of hydrofluoric acid, most of dissolved time of silicon-dioxide is as the criterion.Preferably soak time is not less than 6 hours (time is longer, and silicon-dioxide is dissolved must be more).Leach liquor main component after immersion is silicofluoric acid, after filtration can be for making Sodium Silicofluoride after the clarification.After soaking for the first time, suction filtration goes out soak solution, then adds hydrofluoric acid aqueous solution to soak for the second time.Secondary soak solution, containing most of unreacted hydrofluoric acid, can be used for the immersion hydrofluoric acid aqueous solution soaked as for the first time.
After silicon-dioxide in coal ash part is almost all dissolved, the application clear water soaks (for washing the acid of coal) again, and suction filtration, then steeps with clear water.Regulate the pH value to neutral with micro-alkali.After suction filtration is removed liquid again, the coal obtained is there is no ash or the few pure coal of ash.
To sum up, the invention provides a kind of coal treatment process, the method adopts the acid treatment means that inherent ash in coal is removed, thereby make the pure coal produced hardly containing ash (or ash is extremely low), but after burning exhaust gas dust need not any dust removal installation qualified discharge just, and do not stay the coal ash cinder do not fired.The ash content of coal≤0.8% or lower in the pure coal made through aforesaid method, calorific value of coal >=7500 kilocalorie/kilogram, moisture≤10%, be shaped as fine particle and powder.This pure coal can directly act as a fuel, and during burning, its combustion gases can reach national exhaust gas dust emission standard, combustion fumes≤50mg/m
3, area that therefore can be high in environmental requirement is used.
Embodiment
Referring to specific embodiment, the present invention is described.It will be appreciated by those skilled in the art that these embodiment are only for the present invention is described, the scope that it does not limit the present invention in any way.
Experimental technique in following embodiment if no special instructions, is ordinary method; Test materials used in following embodiment, if no special instructions, be and purchase available from routine biochemistry reagent shop.Wherein, the analytical procedure that in the mensuration ash, the method for oxide content is relevant oxide compound in the GB-7176-2008 chemical analysis method.Before mensuration, the Mg in coal ash, Ca major part exist with the form of carbonate, and the form with MgO, CaO during the calcination post analysis exists.
Embodiment 1
The coal in In A Certain Place of Xinjiang district is originated from employing, and the method according to this invention is produced pure coal.
This ature of coal is: ash approximately 3.5%, fugitive constituent approximately 38%, full sulphur approximately 0.18%.Ash wherein forms in Table 1.
Table 1. ash forms (by weight percentage)
| Al 2O 3 | SiO 2 | Fe 2O 3 | MgO | CaO |
| 13.5% | 46.5% | 12.3% | 1.93% | 1.93% |
At first, feed coal is ground into to particle or the powder below particle diameter 3mm, is placed in the acid resistance pond, then according to oxide compound Al in ash
2O
3, Fe
2O
3, CaO, MgO content add the aqueous hydrochloric acid that concentration is 20 volume %, makes liquid level cover coal fully, immersion treatment 3.5 hours.Suction filtration is removed soak solution, then adds this aqueous hydrochloric acid to soak, and the amount of the aqueous hydrochloric acid that front and back add guarantees to be enough to remove the above-mentioned oxide compound in ash by theory.After analysis is found in coal ash part all to be dissolved by the above-mentioned ash of dissolving with hydrochloric acid, suction filtration goes out soak solution again, adds the clear water washing.
After removing washings, by theory according to SiO in the ash residuum
2Amount, add the hydrofluoric acid aqueous solution that concentration is 10 volume %, make liquid level cover coal fully, immersion treatment 6 hours.Suction filtration is removed soak solution, then adds this hydrofluoric acid aqueous solution to soak, and the amount of the hydrofluoric acid aqueous solution that front and back add guarantees to be enough to remove the SiO in ash by theory
2.Find SiO in coal ash part when analyzing
2All dissolved afterwards again suction filtration by hydrofluoric acid and go out soak solution, add the clear water washing.Then regulate the pH value to neutral with micro-sodium carbonate.Suction filtration is removed washings again, obtains pure coal.
The pure coal obtained is fine particle and Powdered, and its ash content of coal is≤0.3%, and the combustion heating amount is >=7500Kcal/kg, moisture content≤10%.
This kind of pure coal worn into to the coal dust of 250 order fineness, this coal dust burns by detecting exhaust gas dust content≤50mg/m through combustion unit
3.
Embodiment 2
The coal in somewhere, Shaanxi is originated from employing, and the method according to this invention is produced pure coal.
This ature of coal is: ash approximately 5.0%, fugitive constituent approximately 37%, full sulphur approximately 0.22%.Ash wherein forms in Table 2.
Table 2. ash forms (by weight percentage)
| Al 2O 3 | SiO 2 | Fe 2O 3 | MgO | CaO |
| 12.8% | 46.5% | 11.8% | 2.01% | 14.11% |
At first, feed coal is ground into to particle or the powder below particle diameter 3mm, is placed in the acid resistance pond, then according to oxide compound Al in ash
2O
3, Fe
2O
3, CaO, MgO content add the aqueous hydrochloric acid that concentration is 15 volume %, makes liquid level cover coal fully, immersion treatment 4.0 hours.Suction filtration is removed soak solution, then adds this aqueous hydrochloric acid to soak, and the amount of the aqueous hydrochloric acid that front and back add guarantees to be enough to remove the above-mentioned oxide compound in ash by theory.After analysis is found in coal ash part all to be dissolved by the above-mentioned ash of dissolving with hydrochloric acid, suction filtration goes out soak solution again, adds the clear water washing.
After removing washings, according to SiO in the ash residuum
2Amount, add by theory the hydrofluoric acid aqueous solution that concentration is 20 volume %, make liquid level cover coal fully, immersion treatment 6 hours.Suction filtration is removed soak solution, then adds this hydrofluoric acid aqueous solution to soak, and the amount of the hydrofluoric acid aqueous solution that front and back add guarantees to be enough to remove the SiO in ash by theory
2.Find SiO in coal ash part when analyzing
2All dissolved afterwards again suction filtration by hydrofluoric acid and go out soak solution, add the clear water washing.Then regulate the pH value to neutral with micro-sodium bicarbonate.Suction filtration is removed washings again, obtains pure coal.
The pure coal obtained is fine particle and Powdered, and its ash content of coal is≤0.3%, and the combustion heating amount is >=7500Kcal/kg, moisture content≤10%.
This kind of pure coal worn into to the coal dust of 250 order fineness, this coal dust burns by detecting exhaust gas dust content≤50mg/m through combustion unit
3.
Embodiment 3
The coal in somewhere, Inner Mongol is originated from employing, and the method according to this invention is produced pure coal.
This ature of coal is: ash approximately 3.9%, fugitive constituent approximately 35%, full sulphur approximately 0.21%.Ash wherein forms in Table 3.
Table 3. ash forms (by weight percentage)
| Al 2O 3 | SiO 2 | Fe 2O 3 | MgO | CaO |
| 14.8% | 47.5% | 12.1% | 2.15% | 13.85% |
At first, feed coal is ground into to particle or the powder below particle diameter 3mm, is placed in the acid resistance pond, then according to oxide compound Al in ash
2O
3, Fe
2O
3, CaO, MgO content add the aqueous hydrochloric acid that concentration is 10 volume %, makes liquid level cover coal fully, immersion treatment 4.1 hours.Suction filtration is removed soak solution, then adds this aqueous hydrochloric acid to soak, and the amount of the aqueous hydrochloric acid that front and back add guarantees to be enough to remove the above-mentioned oxide compound in ash by theory.After analysis is found in coal ash part all to be dissolved by the above-mentioned ash of dissolving with hydrochloric acid, suction filtration goes out soak solution again, adds the clear water washing.
After removing washings, according to SiO in the ash residuum
2Amount, add the hydrofluoric acid aqueous solution that concentration is 15 volume %, make liquid level cover coal fully, immersion treatment 6 hours.Suction filtration is removed soak solution, then adds this hydrofluoric acid aqueous solution to soak, and the amount of the hydrofluoric acid aqueous solution that front and back add guarantees to be enough to remove the SiO in ash by theory
2.Find SiO in coal ash part when analyzing
2All dissolved afterwards again suction filtration by hydrofluoric acid and go out soak solution, add the clear water washing, with micro-sodium bicarbonate, regulate the pH value to neutral.Suction filtration is removed washings again, obtains pure coal.
The pure coal obtained is fine particle and Powdered, and its ash content of coal is≤0.3%, and the combustion heating amount is >=7500Kcal/kg, moisture content≤10%.
This kind of pure coal worn into to the coal dust of 250 order fineness, this coal dust burns by detecting exhaust gas dust content≤50mg/m through combustion unit
3.
Claims (9)
1. a method of producing pure coal, is characterized in that, described method comprises and adopts respectively hydrochloric acid or aqueous sulfuric acid, hydrofluoric acid aqueous solution to soak successively feed coal to remove the step of ash wherein.
2. method according to claim 1, is characterized in that, said method comprising the steps of:
(1) feed coal is ground into to particle or powder, then with hydrochloric acid or aqueous sulfuric acid, carries out immersion treatment;
(2) remove in step (1) after processing the soak solution formed, use the hydrofluoric acid aqueous solution immersion treatment after washing treated coal with water; And
(3) process the rear soak solution formed in removal step (2), wash treated coal extremely neutral with adjusting PH with base with water, then remove washings.
3. method according to claim 1 and 2, is characterized in that, the ash content of coal in the feed coal of described step (1)≤8 % by weight, preferably≤5 % by weight;
Preferably, total sulphur content in described feed coal≤0.5 % by weight, volatile content >=25 % by weight.
4. according to the method in any one of claims 1 to 3, it is characterized in that, in described step (1), feed coal is ground into to particle or the powder below particle diameter 3mm, then carries out acid treatment.
5. according to the described method of any one in claim 1 to 4, it is characterized in that, in described step (1), the concentration of hydrochloric acid or aqueous sulfuric acid is 10-20 volume %, or is the hydrochloric acid of 4-7N concentration, and the add-on of described hydrochloric acid and/or aqueous sulfuric acid is enough to remove the Al in ash
2O
3, Fe
2O
3, CaO, MgO;
Preferably, immersion treatment 3 hours or more than; Further preferably, twice of immersion treatment or more than.
6. according to the described method of any one in claim 1 to 5, it is characterized in that, the concentration of described hydrofluoric acid aqueous solution is 10-20 volume %, or is the 4-7N concentration unit, and the add-on of described hydrofluoric acid aqueous solution is enough to remove the SiO in ash
2.
7. according to the described method of any one in claim 1 to 6, it is characterized in that, immersion treatment 6 hours or more than; Further preferably, twice of immersion treatment or more than.
8. according to the described method of any one in claim 1 to 7, it is characterized in that, the alkali in described step (3) is selected from Na
2CO
3, NaHCO
3Or NaOH.
9. the pure coal of producing according to the described method of any one in claim 1 to 8.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154165A (en) * | 2015-07-10 | 2015-12-16 | 江苏徐矿能源股份有限公司 | Method for reducing ash in inferior slime |
| CN107674725A (en) * | 2017-10-24 | 2018-02-09 | 六盘水师范学院 | A kind of technique for preparing super clean coal using anthracite chemistry method |
| CN109913283A (en) * | 2019-03-19 | 2019-06-21 | 河南理工大学 | Low order coal dewatering and ash disposal integral system and its working method |
| CN110272772A (en) * | 2019-08-05 | 2019-09-24 | 中南大学 | A kind of ultrapure anthracitic preparation method |
| CN111040820A (en) * | 2019-03-31 | 2020-04-21 | 乐清市智格电子科技有限公司 | Processing technology for improving flame-retardant biomass particles by utilizing micro-nano steam explosion slag |
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| CN102041128A (en) * | 2010-12-03 | 2011-05-04 | 宜宾天原集团股份有限公司 | Chemical deashing method for coal |
| CN102205962A (en) * | 2011-03-10 | 2011-10-05 | 安徽工业大学 | Device and method for preparing activated carbon material for electrochemical capacitor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154165A (en) * | 2015-07-10 | 2015-12-16 | 江苏徐矿能源股份有限公司 | Method for reducing ash in inferior slime |
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| CN107674725A (en) * | 2017-10-24 | 2018-02-09 | 六盘水师范学院 | A kind of technique for preparing super clean coal using anthracite chemistry method |
| CN109913283A (en) * | 2019-03-19 | 2019-06-21 | 河南理工大学 | Low order coal dewatering and ash disposal integral system and its working method |
| CN111040820A (en) * | 2019-03-31 | 2020-04-21 | 乐清市智格电子科技有限公司 | Processing technology for improving flame-retardant biomass particles by utilizing micro-nano steam explosion slag |
| CN111040820B (en) * | 2019-03-31 | 2021-06-29 | 乐清市智格电子科技有限公司 | Processing technology for improving flame-retardant biomass particles by utilizing micro-nano steam explosion slag |
| CN110272772A (en) * | 2019-08-05 | 2019-09-24 | 中南大学 | A kind of ultrapure anthracitic preparation method |
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