CN104178237A - Method for leaching and removing sodium element in coal by using water static pressure - Google Patents
Method for leaching and removing sodium element in coal by using water static pressure Download PDFInfo
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- CN104178237A CN104178237A CN201410395454.3A CN201410395454A CN104178237A CN 104178237 A CN104178237 A CN 104178237A CN 201410395454 A CN201410395454 A CN 201410395454A CN 104178237 A CN104178237 A CN 104178237A
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Abstract
The invention provides a method for leaching and removing sodium in high-sodium coal by using a high-temperature and high-pressure environment generated by water static pressure and an underground heating technology. The method comprises the following steps: levigating coal into a certain size range, so that the formed coal slurry can meet the pumped requirements; pumping the coal slurry into an underground reaction pipe with a certain depth from a ground inlet; enabling the coal slurry to flow inside the pipe at a certain speed, and then pumping out the coal slurry from a ground outlet; and controlling the temperatures of different positions of the reaction pipe to be below a boiling point of water corresponding to the pressure of the position through an underground heating temperature control system. The coal is subjected to change of physical and chemical structures during staying in the underground reaction pipe by using the pressure of the coal slurry and high temperature provided by underground heating, and water-soluble sodium and organic sodium in coal are released from the internal structure of the coal, are dissolved into process water, and then are further removed. According to the technique, low-energy, water-saving and high-efficiency technological approaches are provided for processing and utilizing of the high-sodium coal.
Description
Technical field
The present invention relates to a kind of method that in coal, sodium element leaches and removes, especially relate to a kind of water static pressure that utilizes and realize the method that in coal, sodium element leaches and removes, comprise the one-tenth oar of coal, the technical fields such as the solid-liquid separation of underground High Temperature High Pressure hydrothermal treatment consists, coal and the water of the pumping of coal slurry, coal and water recovery belong to Coal dressing, clean utilization technical field.
Background technology
Alkali metallic sodium is one of inorganic elements main in coal, and in coal ash, the mass percentage content of sodium is (with Na
2o meter) generally below 1.5%, and some low-rank coal, the accurate eastern coal of Xinjiang of China for example, sodium content is more than 5%, have even up to 7%.Sodium content is higher; will cause contamination and the slagging scorification of boiler, affect boiler output, bring harm to the safety and economic operation of power plant; when slagging scorification is serious, also may cause the Serious Accidents such as burner hearth is flame-out, booster, non-programmed halt, to power plant, bring larger financial loss.In addition, basic metal has poisoning effect to the activity of the out of stock catalyzer of SCR, and a large amount of volatile alkali metal compounds can adhere to flying dust and form larger particle, along with flying dust enters flue, not only can result in blockage to catalyzer, and can reduce the work-ing life of catalyzer.For fear of the generation of this class loss, the utilization of power plant to high alkalinity coal, can only mix in right amount and be assigned in the coal that alkali metal content is lower for boiler combustion, has seriously limited the application scale of such coal, causes the applicable surface of such coal narrower.
De-sodium technology is one of major way solving high sodium coal utilization problem, has the active sodium that stains character and be present in the gap structure of coal mainly with the form of water soluble salt or carboxylate salt in coal, can remove by the mode of washing.If open day is on 07 04th, 2012, publication number is in the Chinese patent of CN102533383A, disclosed a kind of high sodium coal takes off sodium decontamination cycle system, and open day is on October 03rd, 2012, publication number is in the Chinese patent of CN202465627U, disclosed a kind of high sodium coal is washed the de-sodium system of ash, all belongs to the water elution sodium technology under different condition; Generally speaking, the water-washing method length consuming time under normal pressure, water loss is large, and de-sodium effect is remarkable not; Although can improve the de-sodium effect under normal pressure by adding some auxiliary agents, cost is higher.And for example open day is on 09 12nd, 2012, publication number is in the Chinese patent of CN102660347A, disclosed a kind of high sodium coal is except sodium technique and system thereof, realize coal under high-temperature and high-pressure conditions in, sodium removes, but be to provide lasting or step high-temperature and high-pressure conditions and need very large energy consumption, and treatment scale amplification difficulty is larger, and practicality is lower.
In sum, also do not have so far the technology of a kind of less energy-consumption, water saving, environmental protection can realize the effective elimination of sodium in high sodium coal.
Summary of the invention
The object of the invention is to overcome above shortcomings in prior art, and provide that a kind of energy consumption is low, water saving, environmental protection, sodium in can effective elimination coal, the water static pressure that utilizes that is conducive to expand high sodium coal utilization scale is realized the method that in coal, sodium element leaches and removes.
The present invention addresses the above problem adopted technical scheme: this utilizes water static pressure to realize the method that in coal, sodium element leaches and removes, and its feature is: the method is applicable to sodium content in coal ash and is greater than 1.5%(w/w, with Na
2o meter) coal, first by raw coal levigate to granularity below 0.2mm, and to be mixed and made into concentration with water be 30%～70%(w/w) coal slurry; Then coal slurry is transported in reacting pipe, and the residence time of coal slurry in reacting pipe is 5～30 minutes, described reacting pipe is positioned at underground, the bottom of this reacting pipe and the distance on ground are 200～1200 meters, utilize the static pressure that in coal slurry, water self produces, be replaced by reaction the lasting needed energy consumption of high pressure is provided, in control reacting pipe, the temperature of coal slurry increases with the increase of the reacting pipe degree of depth, in reacting pipe, the temperature of coal slurry is 80-320 ℃, and coal slurry takes off sodium reaction under high-temperature and high-pressure conditions; The outlet output from reacting pipe by the de-reacted coal slurry of sodium again, and coal slurry is carried out to solid-liquid separation, sodium to be separated with water, thereby obtained the coal after de-sodium, the water of separating utilizes after purifying again.
As preferably, reacting pipe of the present invention is perpendicular to becoming angle between Huo Yu ground, ground.
As preferably, the local existing mine of reacting pipe utilization of the present invention is built, and the outer wall of pipeline is rock or take subsurface rock as support.
As preferably, the entrance and exit of reacting pipe of the present invention is all located at ground, and the entrance and exit pressure of this reacting pipe is normal pressure or low pressure.
As preferably, the present invention, by pumping coal slurry, keeps the mobility of coal slurry in reacting pipe, forms a continuous High Temperature High Pressure hydrothermal treatment process.
As preferably, the present invention adds auxiliary agent in coal slurry, to promote the abundant stripping of sodium.
As preferably, coal slurry of the present invention is mixed to get with water after by dry milling, or directly obtains by wet grinding, or is combined and obtained by dry milling and wet grinding.
As preferably, reacting pipe of the present invention is telescoping or U-shaped tubular type; Described reacting pipe is single reaction tubes, and the caliber of this single reaction tubes is at 0.5～2.5 meter, or described reacting pipe is the mode of a plurality of reaction tubes parallel connections, and to expand coal treatment scale, the quantity of described reaction tubes is in 250.
As preferably, the present invention is electrically heated, microwave heating or gas heating to the underground heating mode of reacting pipe; According to the true pressure of place hot spot or face, by heating and temperature control below boiling point.
As preferably, the entrance and exit of reacting pipe of the present invention is provided with heat exchanger, and this heat exchanger is contactless straight pipe type or coil tube type; Described solid-liquid separation is normal temperature or is less than the middle temperature centrifugation of 100 ℃.
The present invention compared with prior art, has the following advantages and effect: technique is simple, and energy consumption is low, water-saving and environmental protection, and removal efficiency is high, and the sodium in can effective elimination coal, is conducive to expand high sodium coal utilization scale.This high temperature and high pressure environment that utilizes water static pressure and underground heating technology to produce, realize the leaching of sodium in high sodium coal and remove, utilize the pressure of coal slurry self and the high temperature that underground heating provides, make coal retention period in underground reacting pipe that the variation of physics and chemistry structure occur, in coal, water-soluble sodium and organic sodium discharge from the internal structure of coal, be dissolved in process water, then further removed, this technique by the processing and utilization for high sodium coal provide that energy consumption is low, water saving, efficient technological approaches.
The present invention, also can be for other element in coal as the removing of potassium, calcium, magnesium, iron, sulphur in can be used for coal the removing of sodium, widely applicable.The present invention also can utilize other pressuring method, utilizes the static pressure of water simultaneously, reduces the situation of the pressure of entrance and exit, and handiness is good.
Accompanying drawing explanation
Fig. 1 utilizes water static pressure to realize the process flow diagram of the method that in coal, sodium element leaches and removes in the embodiment of the present invention 1.
Embodiment
Below in conjunction with accompanying drawing and by embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1.
Referring to Fig. 1, the characteristic of the high sodium coal raw coal in the present embodiment is as shown in table 1.
Table 1, the former components of coal ash analytical results of high sodium coal table
| Ash component | Na 2O | K 2O | CaO | MgO | Fe 2O 3 | SiO 2 | Al 2O 3 | TiO 2 | SO 2 |
| Content (%) | 6.55 | 0.30 | 30.84 | 6.95 | 8.51 | 13.5 | 6.35 | 0.32 | 19.5 |
Percentage composition in table 1 is quality percentage composition, coal ash analysis result from table 1, Na in this coal ash
2o content 6.55%, CaO content 30.84% and MgO content approximately 6.95%, all far away higher than the common coal in the world, and acidic oxide SiO
2content approximately 13.5%, Al
2o
3content only has 6.35%.The slagging index calculating according to its components of coal ash
r s with dust stratification index
r f be respectively 1.21 and 17.26, belong to moderate slagging scorification, serious dust stratification coal.
In the present embodiment, utilizing water static pressure to realize the method that in coal, sodium element leaches and removes comprises the steps.
A, slurrying: by raw coal levigate to main size-grade distribution between 0.04mm～0.20mm, being mixed and made into concentration with water is 30%(w/w) coal slurry.
B, reaction tubes structure: it is 50cm that coal slurry is pumped into outer tube diameter, and in the telescoping reaction tubes that diameter of inner pipe is 30cm, telescoping reaction tubes is positioned at underground, and reacting pipe total depth is 600m.
C, reaction tubes material: the entrance and exit of reacting pipe is on ground, and the outer wall of outer tube is the high temperature materials such as original rock or pottery.Inner tube is the good steel of heat-conducting effect, keeps pumping into and pumping the sufficient heat exchange of coal slurry.
D, temperature control: adopt electric heating intelligent temperature controlling system, control approximately 300 ℃ of pipeline bottom temps, the degree of depth be 30m with interior reaction zone, temperature is controlled between 270-300 ℃.
E, coal slurry flow velocity: coal slurry is 5m/min at reaction velocity in pipes.
F, sodium remove: the coal slurry pumping from reaction tubes, by whizzer separation, obtain coal dust, and the sodium of leaching is separated with reaction water, and waste water can be recycled after purifying.
The power consumption of said process is about the 5-6% of coal calorific value, and after de-sodium, coal ash ash component analytical results is in Table 2.
Coal ash ash component analytical results table after table 2, de-sodium
| Ash component | Na 2O | K 2O | CaO | MgO | Fe 2O 3 | SiO 2 | Al 2O 3 | TiO 2 | SO 2 |
| Content (%) | 0.72 | 0.19 | 35.01 | 7.57 | 9.61 | 13.3 | 7.54 | 0.36 | 20.1 |
Percentage composition in table 2 is quality percentage composition, and as can be seen from Table 2, after de-sodium is processed, in coal ash, sodium content is reduced to 0.72%, belongs to the scope of low sodium coal.In addition, after treatment in coal butt sulphur content from 0.46% near 0.36%.The slagging index calculating
r s with dust stratification index
r f be respectively 0.90 and 1.80, fouling index greatly reduces.
In the present embodiment, utilize water static pressure to realize the technique of the method that in coal, sodium element leaches and removes simple, energy consumption is low, water saving, environmental protection, and the sodium in can effective elimination coal, is conducive to expand high sodium coal utilization scale.
Embodiment 2.
In the present embodiment, utilize water static pressure to realize the method that in coal, sodium element leaches and removes as follows.
A. applicable coal is that in coal ash, sodium content is greater than 1.5%(w/w, with Na
2o meter) coal.
B. High Temperature High Pressure is acted on to coal slurry, make coal slurry in underground generation hydro-thermal reaction.In coal slurry, the concentration of coal can be 30～70%(w/w).Then coal slurry can be mixed to get with water by dry milling, or directly obtains by wet grinding technology, also can dry type and wet grinding combine and obtain.
C. underground reacting pipe is perpendicular to the angled one or more reacting pipes in Huo Yu ground, ground, can utilize local existing mine etc. to build, the outer wall of pipeline is rock or take subsurface rock as support, and technology requires lower to the high voltage performance of pipeline material.The reacting pipe adopting can be telescoping, U-shaped tubular type etc.By the length of pipeline and the caliber of bottom etc. control coal slurry in residence time of reaction zone at 5～30 minutes.The caliber of single reaction tubes can be at 0.5～2.5 meter.The temperature and pressure that can need according to de-sodium, the design underground pipeline degree of depth is apart from 200～1200 meters, ground.Also can expand coal treatment scale by the mode of a plurality of reaction tubes parallel connections, the quantity of reaction tubes can be between 1-250.
D. the static pressure that utilizes water self to produce, can greatly save as reaction provides and continue the needed energy consumption of high pressure.By water self, provide static pressure, can provide continual pressure for technique.
E. the entrance and exit of reacting pipe is all located at ground, and pressure is normal pressure or low pressure, low to the technical requirements of transferpump.Entrance and exit can arrange and be in the same localities, and also can keep suitable distance, does not arrange and is in the same localities.
F. the pressure being produced by coal slurry self increases gradually with the degree of depth of reacting pipe, and temperature controllable increases with the increase of the degree of depth, and closely surface temperature is lower.By take insulation and the heat exchanger of gangway can a nearly step save energy at reacting pipe outer wall.In underground pipeline, coal slurry temperature is generally 80-320 ℃, and exit coal slurry temperature is generally room temperature to 80 ℃; To the underground heating mode of reacting pipe, can be electrically heated, microwave heating, gas heating etc.; According to the true pressure of place hot spot or face, temperature is controlled at below boiling point; Can realize by intelligent temperature control system; The heat exchanger of gangway can be contactless straight pipe type, coil tube type etc.
G. the coal slurry pumping from outlet, by solid-liquid separation technique, is separated sodium with liquid water.Solid-liquid separation technique, can dehydrate technology for non-evaporatings such as normal temperature or middle temperature (being less than 100 degree) centrifugation, pressure filtrations.
H. containing sodium water, can recycle by purifying treatment.
I. by pumping coal slurry, keep the mobility of coal slurry in reacting pipe, form a continuous High Temperature High Pressure hydrothermal treatment process.For guaranteeing stability and the mobility of coal slurry, can suitably add the auxiliary agents such as stablizer.
J. according to practical situation, can in coal slurry, add appropriate auxiliary agent, promote the abundant stripping of sodium.Do not use additive also can reach de-sodium effect, also can reduce the reacting pipe degree of depth and temperature of reaction by adding auxiliary agent, thereby reduce construction investment, the auxiliary agent of interpolation comprises solubility promoter, decarboxylating agent etc.
In the present embodiment, utilize water static pressure to realize the technique of the method that in coal, sodium element leaches and removes simple, energy consumption is low, water-saving and environmental protection, and removal efficiency is high, and the sodium in can effective elimination coal, is conducive to expand high sodium coal utilization scale.
Embodiment 3.
In the present embodiment, utilize water static pressure to realize method that in coal, sodium element leaches and removes and be applicable to sodium content in coal ash and be greater than 1.5%(w/w, with Na
2o meter) coal, the method first by raw coal levigate to granularity below 0.2mm, and to be mixed and made into concentration with water be 30%～70%(w/w) coal slurry; Then coal slurry is transported in reacting pipe, and the residence time of coal slurry in reacting pipe is 5～30 minutes, described reacting pipe is positioned at underground, the bottom of this reacting pipe and the distance on ground are 200～1200 meters, utilize the static pressure that in coal slurry, water self produces, be replaced by reaction the lasting needed energy consumption of high pressure is provided, in control reacting pipe, the temperature of coal slurry increases with the increase of the reacting pipe degree of depth, in reacting pipe, the temperature of coal slurry is 80-320 ℃, and coal slurry takes off sodium reaction under high-temperature and high-pressure conditions; The outlet output from reacting pipe by the de-reacted coal slurry of sodium again, and coal slurry is carried out to solid-liquid separation, sodium to be separated with water, thereby obtained the coal after de-sodium, the water of separating utilizes after purifying again.
Reacting pipe in the present embodiment can be perpendicular to becoming angle between Huo Yu ground, ground.Reacting pipe can utilize local existing mine to build, and the outer wall of pipeline is rock or take subsurface rock as support.The entrance and exit of reacting pipe all can be located at ground, and the entrance and exit pressure of this reacting pipe is normal pressure or low pressure.Can keep the mobility of coal slurry in reacting pipe by pumping coal slurry, form a continuous High Temperature High Pressure hydrothermal treatment process.Can in coal slurry, add auxiliary agent, to promote the abundant stripping of sodium.Coal slurry can be by being mixed to get with water after dry milling, or directly obtain by wet grinding, or combined and obtained by dry milling and wet grinding.
Reacting pipe in the present embodiment can be telescoping or U-shaped tubular type; Reacting pipe can be single reaction tubes, and the caliber of this single reaction tubes is at 0.5～2.5 meter, or reacting pipe can be also the mode of a plurality of reaction tubes parallel connections, and to expand coal treatment scale, the quantity of reaction tubes is in 250.To the underground heating mode of reacting pipe, can be electrically heated, microwave heating or gas heating; According to the true pressure of place hot spot or face, by heating and temperature control below boiling point.The entrance and exit of reacting pipe can be provided with heat exchanger, and this heat exchanger is contactless straight pipe type or coil tube type; Described solid-liquid separation is normal temperature or is less than the middle temperature centrifugation of 100 ℃.
In the present embodiment, utilize water static pressure to realize the technique of the method that in coal, sodium element leaches and removes simple, energy consumption is low, water saving, environmental protection, and the sodium in can effective elimination coal, is conducive to expand high sodium coal utilization scale.
Although the present invention with embodiment openly as above; but it is not in order to limit protection scope of the present invention; any technician who is familiar with this technology, not departing from change and the retouching of doing in the spirit and scope of the present invention, all should belong to protection scope of the present invention.
Claims (10)
1. utilize water static pressure to realize the method that in coal, sodium element leaches and removes, it is characterized in that: the method is applicable to sodium content in coal ash and is greater than 1.5%(w/w, with Na
2o meter) coal, first by raw coal levigate to granularity below 0.2mm, and to be mixed and made into concentration with water be 30%～70%(w/w) coal slurry; Then coal slurry is transported in reacting pipe, and the residence time of coal slurry in reacting pipe is 5～30 minutes, described reacting pipe is positioned at underground, the bottom of this reacting pipe and the distance on ground are 200～1200 meters, utilize the static pressure that in coal slurry, water self produces, be replaced by reaction the lasting needed energy consumption of high pressure is provided, in control reacting pipe, the temperature of coal slurry increases with the increase of the reacting pipe degree of depth, in reacting pipe, the temperature of coal slurry is 80-320 ℃, and coal slurry takes off sodium reaction under high-temperature and high-pressure conditions; The outlet output from reacting pipe by the de-reacted coal slurry of sodium again, and coal slurry is carried out to solid-liquid separation, sodium to be separated with water, thereby obtained the coal after de-sodium, the water of separating utilizes after purifying again.
2. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: described reacting pipe is perpendicular to becoming angle between Huo Yu ground, ground.
3. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: the local existing mine of described reacting pipe utilization is built, and the outer wall of pipeline is rock or take subsurface rock as support.
4. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: the entrance and exit of described reacting pipe is all located at ground, and the entrance and exit pressure of this reacting pipe is normal pressure or low pressure.
5. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: by pumping coal slurry, keep the mobility of coal slurry in reacting pipe, form a continuous High Temperature High Pressure hydrothermal treatment process.
6. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: in coal slurry, add auxiliary agent, to promote the abundant stripping of sodium.
7. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, it is characterized in that: described coal slurry is mixed to get with water after by dry milling, or directly obtain by wet grinding, or combine and obtain by dry milling and wet grinding.
8. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: described reacting pipe is telescoping or U-shaped tubular type; Described reacting pipe is single reaction tubes, and the caliber of this single reaction tubes is at 0.5～2.5 meter, or described reacting pipe is the mode of a plurality of reaction tubes parallel connections, and to expand coal treatment scale, the quantity of described reaction tubes is in 250.
9. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, and it is characterized in that: to the underground heating mode of reacting pipe, be electrically heated, microwave heating or gas heating; According to the true pressure of place hot spot or face, by heating and temperature control below boiling point.
10. the water static pressure that utilizes according to claim 1 is realized the method that in coal, sodium element leaches and removes, it is characterized in that: the entrance and exit of described reacting pipe is provided with heat exchanger, this heat exchanger is contactless straight pipe type or coil tube type; Described solid-liquid separation is normal temperature or is less than the middle temperature centrifugation of 100 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136548A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Steam type high-temperature leaching device |
| CN109136547A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Continuous high-temperature leaching device |
| CN109126681A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Pipeline vibrating material reaction unit |
| CN114314626A (en) * | 2022-01-19 | 2022-04-12 | 湖南绿脉环保科技股份有限公司 | Method for reducing sodium content in fluorine-containing raw material |
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| US3973628A (en) * | 1975-04-30 | 1976-08-10 | New Mexico Tech Research Foundation | In situ solution mining of coal |
| CN102660347A (en) * | 2012-05-08 | 2012-09-12 | 中国五环工程有限公司 | Process for removing sodium in high-sodium coal and system thereof |
| CN103131501A (en) * | 2013-03-22 | 2013-06-05 | 施大钟 | Intermittent sodium removal and purification method for high-sodium coal |
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2014
- 2014-08-13 CN CN201410395454.3A patent/CN104178237B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3973628A (en) * | 1975-04-30 | 1976-08-10 | New Mexico Tech Research Foundation | In situ solution mining of coal |
| CN102660347A (en) * | 2012-05-08 | 2012-09-12 | 中国五环工程有限公司 | Process for removing sodium in high-sodium coal and system thereof |
| CN103131501A (en) * | 2013-03-22 | 2013-06-05 | 施大钟 | Intermittent sodium removal and purification method for high-sodium coal |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136548A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Steam type high-temperature leaching device |
| CN109136547A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Continuous high-temperature leaching device |
| CN109126681A (en) * | 2018-10-16 | 2019-01-04 | 湖南行者环保科技有限公司 | Pipeline vibrating material reaction unit |
| CN114314626A (en) * | 2022-01-19 | 2022-04-12 | 湖南绿脉环保科技股份有限公司 | Method for reducing sodium content in fluorine-containing raw material |
| CN114314626B (en) * | 2022-01-19 | 2024-01-26 | 湖南绿脉环保科技股份有限公司 | Method for reducing sodium content in fluorine-containing raw material |
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| CN104178237B (en) | 2016-08-31 |
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