CN103421560A - Coal-based heavy fuel oil and production method thereof - Google Patents
Coal-based heavy fuel oil and production method thereof Download PDFInfo
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- CN103421560A CN103421560A CN2013100102091A CN201310010209A CN103421560A CN 103421560 A CN103421560 A CN 103421560A CN 2013100102091 A CN2013100102091 A CN 2013100102091A CN 201310010209 A CN201310010209 A CN 201310010209A CN 103421560 A CN103421560 A CN 103421560A
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Abstract
The invention provides a production method of coal-based heavy fuel oil, which comprises the following steps: respectively and sequentially soaking feed coal with an aqueous solution hydrochloric acid or sulfuric acid aqueous solution and an aqueous solution of hydrofluoric acid to remove ash in the feed coal, and then mixing the processed feed coal and oil. The coal-based fuel oil is high in burning heat, flue gas and dust, produced after the burning, can reach the emission standard, without any dust removal equipment, noncombustible ash and cinder are not left, the coal-based fuel oil can be used in regions with high environment-protection requirement, and the condition of fuel shortage can be beneficial for being alleviated.
Description
Technical field
The invention belongs to the fuel making field, particularly, the present invention relates to a kind of coal derived fuel heavy oil 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.
Also developed at present the method that coal is replaced after treatment to oil fuel.But equally because ash in coal is large, make this fuel cause than overall situation and pollute, therefore can't directly apply.
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 the pure coal obtained can be used in the fuel that preparation replaces oil fuel or fuel heavy oil, thereby the reduction energy consumption, 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 method of producing coal derived fuel heavy oil, the method adopts pure coal and the oils of having removed ash to be mixed with fuel heavy oil, due to this pure coal hardly containing ash (or ash is extremely low), but so this coal derived fuel heavy oil after burning, flue gas can be without dust removal installation qualified discharge just.
Particularly, the invention provides following technical scheme:
On the one hand, the invention provides a kind of method of producing coal derived fuel heavy oil, the method comprises: adopt respectively hydrochloric acid or aqueous sulfuric acid, hydrofluoric acid aqueous solution to soak successively feed coal to remove ash wherein, then treated coal is mixed with oils.
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;
(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; And
(4) treated coal step (3) obtained mixes with oils, and wears into slurry.
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.
In addition, the oils in described step (4) be selected from oil that damaged tire produces, refinery inferior horn oil, remove impurity used oil, remove impurity waste vegetable oil, produce one or more in the vegetables oil reclaimed in the charcoal process;
Preferably, in described step (4), the ratio with 3:1 mixes treated coal and oils;
Further preferably, described step (4) also comprises the mixture of treated coal and oils is ground to form to slurry.
On the other hand, the present invention also provides the coal derived fuel heavy oil 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.
The pure coal produced with aforesaid method can be made the fuel heavy oil suitable with current performance of heavy oil.Concrete steps comprise: the above-mentioned pure coal of take is main raw material, adds 10 ~ 40% the cheap oil plant that can thoroughly burn, and this oil plant is the plant refiltered oil for example, biofuel, the by-product oil in oil production, the used oil of treated mistake etc.By mixture ball milling in ball mill, until the slurry of wearing into can layering and precipitating.Thereby obtain the very approaching coal derived fuel heavy oil of face shaping, combustionproperty and fuel heavy oil.Can on existing fuel heavy oil device, prepare by this heavy oil, can petroleum replacing heavy oil, and city that also can be high in environmental requirement is for substituting other fuel oil or gas fuel.
To sum up, the invention provides a kind of production method of coal derived fuel heavy oil, 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 is mixed to the coal derived fuel heavy oil combustion heat made with oils high, but and after burning exhaust gas dust need not any dust removal installation qualified discharge just, and not staying the coal ash cinder do not fired, area that can be high in environmental requirement is used, and contributes to alleviate the problem of oil fuel anxiety.
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 coal derived fuel heavy oil.
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, with micro-sodium carbonate, 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.
By pure coal and the cheap oil plant of choosing (oil that damaged tire is produced, the inferior horn of refinery oil, remove impurity used oil, remove impurity waste vegetable oil, produce the vegetables oil reclaimed in the charcoal process) mix, mixture ratio is pure coal: oil=3:1.Mixture is placed in to grinding in ball grinder, until form not stratified slurry, thus obtain coal derived fuel heavy oil of the present invention.
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
2Almost all 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.
By pure coal and the cheap oil plant of choosing (oil that damaged tire is produced, the inferior horn of refinery oil, remove impurity used oil, remove impurity waste vegetable oil, produce the vegetables oil reclaimed in the charcoal process) mix, mixture ratio is pure coal: oil=3:1.Mixture is placed in to grinding in ball grinder, until form not stratified slurry, thus obtain coal derived fuel heavy oil of the present invention.
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 almost all to be dissolved by the 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
2Almost all 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.
By pure coal and the cheap oil plant of choosing (oil that damaged tire is produced, the inferior horn of refinery oil, remove impurity used oil, remove impurity waste vegetable oil, produce the vegetables oil reclaimed in the charcoal process) mix, mixture ratio is pure coal: oil=3:1.Mixture is placed in to grinding in ball grinder, until form not stratified slurry, thus obtain coal derived fuel heavy oil of the present invention.
Claims (9)
1. a method of producing coal derived fuel heavy oil, is characterized in that, described method comprises: adopt respectively hydrochloric acid or aqueous sulfuric acid, hydrofluoric acid aqueous solution to soak successively feed coal to remove ash wherein, then treated coal is mixed with oils.
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;
(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; And
(4) treated coal step (3) obtained mixes with oils, and wears into slurry.
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;
Preferably, 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.
5. according to the described method of any one in claim 1 to 4, it is characterized in that, in described 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
2
Preferably, immersion treatment 6 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 alkali in described step (3) is selected from Na
2CO
3, NaHCO
3Or NaOH.
7. according to the described method of any one in claim 1 to 6, it is characterized in that, the oils in described step (4) be selected from oil that damaged tire produces, refinery inferior horn oil, remove impurity used oil, remove impurity waste vegetable oil, produce one or more in the vegetables oil reclaimed in the charcoal process.
8. according to the described method of any one in claim 1 to 7, it is characterized in that, the ratio with 3:1 in described step (4) mixes treated coal and oils;
Preferably, described step (4) also comprises the mixture of treated coal and oils is ground to form to slurry.
9. the coal derived fuel heavy oil of producing according to the described method of any one in claim 1 to 8.
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|---|---|---|---|
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|---|---|---|---|
| CN201310010209.1A CN103421560B (en) | 2013-01-10 | 2013-01-10 | Coal-based heavy fuel oil and production method thereof |
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| CN103421560B CN103421560B (en) | 2015-07-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203608A (en) * | 2017-12-21 | 2018-06-26 | 北京三聚环保新材料股份有限公司 | A kind of method for improving coal solid content |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931971A (en) * | 2006-09-07 | 2007-03-21 | 刘世义 | Fuel slurry preparing process |
| 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 |
-
2013
- 2013-01-10 CN CN201310010209.1A patent/CN103421560B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931971A (en) * | 2006-09-07 | 2007-03-21 | 刘世义 | Fuel slurry preparing process |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203608A (en) * | 2017-12-21 | 2018-06-26 | 北京三聚环保新材料股份有限公司 | A kind of method for improving coal solid content |
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