CN112266808A - Desulfurization method for oxidized coal by electro-Fenton-iron reduction method - Google Patents
Desulfurization method for oxidized coal by electro-Fenton-iron reduction method Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L9/02—Treating solid fuels to improve their combustion by chemical means
- C10L9/06—Treating solid fuels to improve their combustion by chemical means by oxidation
Abstract
The invention relates to a desulfurization method of oxidized coal by an electro-Fenton-iron reduction method, which comprises the steps of adding a certain proportion of water into the coal, and grinding the coal into coal water slurry with qualified particle size; mixing the coal water slurry with FeSO4After the solutions are fully mixed, standing for 1-2 h, and mixing with hydrogen peroxide and acid liquor in a diaphragm-free electrolytic cell to form a Fenton reagent oxidation system; carrying out electrochemical reaction on a Fenton reagent oxidation system to obtain desulfurized coal water slurry; and washing the desulfurized coal water slurry to be neutral, filtering and drying to obtain desulfurized coal powder. The coal desulfurization method provided by the invention only needs to add a small amount of chemical reagent to treat high-sulfur coal dust, and the desulfurization rate can reach 40-50% after treatment. The energy consumption is low, and the treatment cost can be greatly reduced; and the equipment is relatively simple, the post-treatment is simple, the automatic control is easy to realize, the environment is friendly, and the method is suitable for large-scale industrialization.
Description
Technical Field
The invention relates to the field of electrochemical advanced oxidation technology (AOPs) desulfurization, in particular to the technical field of removing coal fuel with high sulfur content by oxidizing hydroxyl free radicals with strong oxidizing property generated by an electro-Fenton method.
Background
China is the only world large energy consumption country mainly using coal, coal occupies more than half of the national energy production and consumption, coal consumption occupies more than 20% of the world total coal consumption, and most of China's high-sulfur coal is used for combustion, so that the pollution of sulfur oxides is reduced and controlled, and the state gives policies and measures for limiting wax and stopping production of the high-sulfur coal in time, so that the atmospheric pollution is reduced and relieved undoubtedly in the near future; however, high-sulfur coal is still an important coal resource in China, and the high-sulfur coal in China has complete varieties, namely high-sulfur lignite and bituminous coal, and also high-sulfur anthracite. Most of sulfur in the high-sulfur coal exists in the form of pyrite, a few high-sulfur coals mainly containing organic sulfur are found, the reserves of the high-sulfur coal in China are considerable, and various desulfurization technologies are sought to meet the utilization of the high-sulfur coal in different use environments.
The problem of high sulfur of coal-based fuels is solved, and besides the development and application of some desulfurization technologies in the use process of the coal-based fuels, the development of direct desulfurization technologies for the coal-based fuels is also necessary.
Most of sulfur in coal fuel is organic sulfur bonded by carbon bond, and the reported methods for direct desulfurization of coal fuel include high-temperature calcination, solvent extraction desulfurization, chemical treatment of alkali metal compounds, hydrodesulfurization, desulfurization in vacuum, and the like. (1) High temperature calcination, the C-S bond energy in solid fuels is high and not prone to break, so desulfurization of coal fuels at 1400 ℃ or higher is the most direct and efficientA method. The higher the temperature in the calcining process is, the higher the desulfurization rate is, on one hand, the performance of calcined coke is influenced, and on the other hand, the energy consumption is high and the desulfurization cost is high. (2) The solvent extraction desulfurization utilizes the principle of similar intermiscibility and uses similar compounds as impregnating solvents, the flow is simple, but the desulfurization rate is low and generally does not exceed 20 percent, and the industrial scale application difficulty is large. (3) Hydrodesulfurization is to heat coal by using a fixed bed and introduce hydrogen, wherein the higher the temperature is, the better the desulfurization effect is, and the reaction temperature is more than one thousand degrees. (4) The coal fuel is desulfurized in vacuum, and is kept for 2 hours at 1500 ℃, the particle size is-150 mm, and the vacuum degree is 1 pa. The vacuum degree improves the desulfurization efficiency. More importantly, the SO in the traditional desulfurization process can be replaced by high-temperature calcination2And (5) discharging. When the desulfurization method is applied, the problems of energy consumption, hydrogen consumption or unsuitability for large-scale industrialization respectively exist, and the industrial implementation is limited.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a desulfurization method for oxidized coal by an electro-Fenton-iron reduction method, which aims to solve the problems of energy consumption, hydrogen consumption or unsuitability for large-scale industrialization of the existing desulfurization method.
The technical scheme is as follows:
a desulfurization method for oxidized coal by an electro-Fenton-iron reduction method comprises the following steps:
(1) adding water into coal in a certain proportion, and grinding the coal into coal water slurry with qualified particle size;
(2) mixing the coal water slurry obtained in the step (1) with FeSO4After the solutions are fully mixed, standing for 1-2 h, and mixing with hydrogen peroxide and acid liquor in a diaphragm-free electrolytic cell to form a Fenton reagent oxidation system;
(3) carrying out electrochemical reaction on the Fenton reagent oxidation system in the step (2) to obtain desulfurized coal water slurry;
(4) and (4) washing the desulfurized coal water slurry in the step (3) to be neutral, filtering and drying to obtain desulfurized coal powder.
In the step (1), water with a certain proportion is added according to the mass ratio of 50% +/-5% of coal.
The coal water slurry with qualified particle size in the step (1) is ground to prepare coal water slurry with particle size of 50-180 um.
The molar concentration of the hydrogen peroxide in the step (2) is 0.0546 mol/L-0.12 mol/L.
FeSO in step (2)4The solution is FeSO4·7H20 solution, FeSO4·7H20 is added in the amount of H in premix2O2Measured in a molar ratio of H2O2:Fe2+＝70:1～7。
And (3) in the step (2), the acid solution is sulfuric acid or hydrochloric acid, and the pH value of a mixed system of the Fenton reagent and the coal water slurry is adjusted to be 3 +/-0.5.
In the step (2), the diaphragm-free electrolytic cell and diaphragm-free electrolytic cell electrodes use stainless steel as cathodes and graphite as anodes, the distance between electrode plates of the cathodes and the anodes is 8-10 cm, two ends of the cathodes and the anodes are connected with a direct current power supply, and air is introduced below the electrolytic cell.
In the step (3), the electrochemical reaction time is 3-5 h, the electrolytic voltage is 3-8V, the air flow is 1.5-2.5L/min, and the current density is 10-20 mA/cm3。
The advantages and effects are as follows:
the invention utilizes electro-Fenton-iron reduction method to produce OH which is used as oxidant to oxidize and remove sulfur in coal. The coal desulfurization method provided by the invention only needs to add a small amount of chemical reagent to treat high-sulfur coal dust, and the desulfurization rate can reach 40-50% after treatment. The energy consumption is low, and the treatment cost can be greatly reduced; and the equipment is relatively simple, the post-treatment is simple, the automatic control is easy to realize, the environment is friendly, and the method is suitable for large-scale industrialization.
Drawings
FIG. 1 is a chart of an infrared spectrum of coal before desulfurization;
FIG. 2 is an infrared spectrum of the desulfurized coal obtained by the method.
Detailed Description
The present invention and other features will be described in more detail below.
The electro-Fenton method (electric-Fenton pro eess) started in the 80 s of the 20 th century and was an electrochemical reaction based on Fenton (Fenton) chemical reaction developed in the water treatment technology in recent yearsAdvanced oxidation technology. The invention adopts an electro-Fenton-iron reduction method, and H can be added into a Fenton reagent from the outside in an acidic medium in the electrochemical process2O2And Fe2+Or electrochemically producing Fe2+And H2O2As a continuous source of the Fenton reagent, the added reagent is saved, in particular the additional H in the Fenton reagent2O2And through O2Two electrons are reduced at the cathode to generate H2O2，H2O2Can quickly react with the added Fe in the solution2+Generates Fenton reaction and generates OH and Fe with strong oxidizing capability3+And is of Fe3+Can be reduced to Fe at the cathode2+Reduced to obtain Fe2+Can be used as a continuous source of Fenton reagent, and the OH with strong oxidizing capability is produced by the reaction to oxidize and remove the sulfur in the coal.
The desulfurization and purification process of the oxidized coal by the electro-Fenton method is obviously characterized by being carried out at normal pressure and normal temperature; the desulfurization oxidant OH is generated in the reaction process, is easy to obtain and has low cost; the electrolysis process does not produce secondary pollution; only the current, the voltage and the aeration quantity need to be controlled in the electrolysis process. The automatic control is convenient to realize; has the advantages of simple operation process, low energy consumption, environmental protection and the like. Provides an effective method for the oxidative desulfurization of coal.
A desulfurization method for oxidized coal by an electro-Fenton-iron reduction method comprises the following steps:
(1) adding coal into water with a certain proportion, and grinding the mixture into water-coal-slurry with qualified particle size in a wet ball mill;
(2) mixing the coal water slurry obtained in the step (1) with FeSO4After the solution is fully mixed in a stirring tank, standing for 1-2 h, mixing the solution with hydrogen peroxide and acid liquor in a diaphragm-free electrolytic tank to prepare a Fenton reagent oxidation system;
(3) under the conditions of controlling and stabilizing current, adjusting voltage and air quantity, the electrolytic cell performs electrochemical reaction on the Fenton reagent oxidation system in the step (2), namely electrolytic oxidation desulfurization reaction, so as to obtain desulfurized coal water slurry;
(4) and (4) washing the desulfurized coal water slurry in the step (3) to be neutral, filtering and drying, namely filtering solid substances from the coal water slurry, separating filtrate and drying to obtain desulfurized coal powder.
The water in the invention is tap water, the cost of the tap water is lower, and the experimental result is not influenced. Other higher purity waters (deionized water, purified water, etc.) are equally suitable, but at higher cost.
In the step (1), water with a certain proportion is added according to the mass ratio of 50% +/-5% of the solid.
The coal water slurry with qualified particle size in the step (1) is ground to prepare coal water slurry with particle size of 50-180 um.
The addition amount of the hydrogen peroxide in the step (2) is that H in the solution of the Fenton reagent is added during the blending of the electrolyte according to the Fenton reagent2O2The molar concentration is 0.0529 mol/L-0.22 mol/L, the acid solution is sulfuric acid or hydrochloric acid, and the pH of the Fenton reagent oxidation system is adjusted to be 3 +/-0.5.
FeSO in step (2)4The solution is FeSO4·7H20 amount of solution added as premixed H2O2Measured in a molar ratio of H2O2:Fe2+＝70:1～7。
In the step (2), a non-isolated electrolytic cell is adopted as the diaphragm-free electrolytic cell, stainless steel is used as a cathode and graphite is used as an anode for an electrode of the diaphragm-free electrolytic cell, the distance between electrode plates of the cathode and the anode is 8-10 cm, a direct current power supply is connected to two ends of the cathode and the anode, the voltage is adjusted, the current is controlled to be stabilized at a certain value, and air is introduced below the electrolytic cell and the air flow is controlled to play a role in stirring.
In the step (3), the electrochemical reaction time is 3-5 h, the electrolytic voltage is 3-8V, the air flow is 1.5-2.5L/min, and the current density is 10-20 mA/cm3。
30% H in oxidation system by electro-Fenton method2O2The adding amount is 6-10% of the mass of the coal water slurry. Namely, control of H in Fenton's reagent solution2O2The molar concentration is 0.0529 mol/L-0.22 mol/L.
The final mass percentage of coal in the electrolyte and coal water slurry mixed solution of the electro-Fenton method is 20-30%.
The first embodiment is as follows:
the sulfur content of the high-sulfur clean coal is 3.12%, 680g of the high-sulfur clean coal is taken and milled for 60min by a wet method of adding 340ml of water into 370-380 r/min of a ball mill, and the coal water slurry is prepared, wherein the particle size distribution (measured after the coal slurry is dried) range is mainly 50-180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O28.41g in mass, and standing for 1h after mixing and stirring with the coal water slurry.
30% of H2O2The adding amount is 6 percent calculated by the total mass of the coal water slurry.
The final mass percent of water in the coal water slurry mixed solution is 90.79%.
The pH was adjusted to 2.5 with sulfuric acid.
Controlling the electrolytic voltage to be 3.0V, the air flow to be 1.5L/min and the current density to be 10mA/cm3The reaction time is 3 h.
After the oxidation is finished, fine coal powder is filtered from the electrolyte.
Washing the fine coal powder filtered after oxidation and desulfurization with tap water to neutrality, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214-2007 method for measuring total sulfur in coal, and the sulfur content of the high-sulfur clean coal before treatment is 3.12%, the average sulfur content of the desulfurized clean coal is 1.835%, and the desulfurization rate is 41.2% under the above experimental conditions.
Example two:
the sulfur content of the high-sulfur clean coal is 2.56%, 1700g of the high-sulfur clean coal is taken out and is ground by a ball mill with 370-380 r/min and 850ml of water for 60min by a wet method, and the water-coal-slurry is prepared, wherein the particle size distribution (measured after the coal-slurry is dried) range is mainly 50-180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O2245.29g in mass, and standing for 2 hours after mixing and stirring with the coal water slurry.
30% of H2O2The adding amount is 10 percent of the total mass of the coal water slurry.
The final mass percent of water in the coal water slurry mixed solution is 74.93%.
The pH was adjusted to 2.5 with sulfuric acid.
Controlling electrolysisVoltage 8V, air flow 2.5L/min, current density 20mA/cm3The reaction time is 4 h.
And after the oxidation is finished, filtering coal powder from the coal water slurry.
Washing the filtered coal powder after oxidative desulfurization to be neutral by tap water, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214-2007 method for measuring total sulfur in coal, and the sulfur content of the high-sulfur clean coal before treatment is 2.56%, the average sulfur content of the desulfurized high-sulfur clean coal is 1.4%, and the desulfurization rate is 45.3% under the above experimental conditions.
Example three:
the sulfur content of the high-sulfur coal is 3.0%, 680g of the high-sulfur coal is taken and milled for 60min by a wet method of adding 340ml of water into 370-380 r/min of a ball mill, and the coal water slurry is prepared, wherein the particle size distribution (measured after the coal slurry is dried) range is mainly 50-180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O28.41g in mass, and standing for 1.5 hours after mixing and stirring with the coal water slurry.
30% of H2O2The adding amount is 6 percent calculated by the total mass of the coal water slurry.
The final mass percent of water in the coal water slurry mixed solution is 90.79%.
The pH was adjusted to 3.5 with sulfuric acid.
Controlling the electrolytic voltage to be 3.3V, the air flow to be 1.5L/min and the current density to be 10mA/cm3The reaction time is 3 h.
And after the oxidation is finished, filtering the coal powder from the electrolyte.
Washing the filtered coal powder after oxidation and desulfurization with tap water to neutrality, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214 plus 2007 method for measuring total sulfur in coal, and the sulfur content of the high-sulfur clean coal before treatment is 3.0%, the average sulfur content of the desulfurized high-sulfur clean coal is 1.779%, and the desulfurization rate is 40.7% under the experimental conditions.
Example four:
the sulfur content of the high-sulfur coal is 2.5 percent, 1700g of the high-sulfur coal is taken and milled by a ball mill with 370 to 380r/min and 850ml of water for 60min by a wet method, and the water-coal-slurry is prepared, wherein the particle size distribution (measured after the coal-slurry is dried) range is mainly 50 to 180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O2245.29g in mass, and standing for 2 hours after mixing and stirring with the coal water slurry.
30% of H2O2The adding amount is 10 percent of the total mass of the coal water slurry.
The final mass percent of water in the coal slurry mixed solution is 74.93%.
The pH was adjusted to 2.5 with sulfuric acid.
Controlling electrolysis voltage of 8V, air flow of 2.5L/min, and current density of 20mA/cm3The reaction time is 4 h.
And after the oxidation is finished, filtering the coal powder from the coal slurry.
Washing the filtered coal powder after oxidative desulfurization to be neutral by tap water, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214-2007 method for measuring total sulfur in coal, and the sulfur content of the high-sulfur clean coal before treatment is 2.5%, the average sulfur content of the desulfurized coal is 1.39%, and the desulfurization rate is 44.5% under the above experimental conditions.
Example five:
the sulfur content of the high-sulfur clean coal is 2.5%, 340g of the high-sulfur clean coal is taken out and is subjected to wet grinding for 60min by adding 170ml of water at 370-380 r/min by a ball mill, and the coal slurry is prepared, wherein the particle size distribution range is mainly 50-180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O29.6g by mass, and standing for 2 hours after mixing and stirring with the coal slurry.
30% of H2O2The adding amount is 7.2 percent calculated by the total mass of the coal slurry.
The final mass percent of water in the coal slurry mixed solution is 94.27%.
The pH was adjusted to 3 with sulfuric acid.
Controlling the electrolytic voltage to be 6.3V, the air flow to be 2L/min and the current density to be 20mA/cm3The reaction time is 4 h.
And after the oxidation is finished, filtering the coal powder from the coal slurry.
Washing the oxidized and desulfurized coal powder to neutrality, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214-2007 method for measuring total sulfur in coal, and the sulfur content of the clean coal before treatment is 2.5%, the average sulfur content of the clean coal after desulfurization is 1.125%, and the desulfurization rate is 55% under the above experimental conditions.
Comparative examples
The sulfur content of certain domestic clean coal is 1.5%, 340g of coal sample is accurately weighed, the coal sample is ground and sieved to be below 200 meshes, the coal sample is placed in an electrolytic cell, electrolyte solution is added, a constant-speed aerating device is used for stirring the coal sample evenly to form coal water slurry, and a power supply is switched on. The current is 1.0A, the coal slurry concentration is 0.03g/mL, the electrolyte concentration is 0.4mo1/L, and the electrolysis time is 6 h. And repeatedly washing the electrode with deionized water until the electrode is neutral, filtering, washing, drying and weighing. The sulfur content of the electrolyzed clean coal is measured to be 1.134 percent, and the removal rate is 20.5 percent.
The experimental method
1.5 percent of sulfur content of certain domestic coal (the same as coal used in a comparison experiment), 340g of coal is taken and milled for 60min by a wet method of adding 170ml of water into 370-380 r/min of a ball mill, and the particle size distribution range is mainly 50-180 um.
Weighing FeSO4(·7H2O), the addition amount is H2O29.6g by mass, and standing for 2 hours after mixing and stirring with the coal slurry.
30% of H2O2The adding amount is 7.2 percent calculated by the total mass of the coal slurry.
The final mass percent of water in the coal slurry mixed solution is 94.27%.
The pH was adjusted to 3 with sulfuric acid.
Controlling the electrolytic voltage to be 7V, the air flow to be 2.5L/min and the current density to be 20mA/cm3The reaction time is 3 h.
And after the oxidation is finished, filtering the coal powder from the coal slurry.
Washing the oxidized and desulfurized coal powder to neutrality, filtering and drying.
The sulfur content of the desulfurized pulverized coal is measured according to GB/T214-2007 method for measuring total sulfur in coal, and the sulfur content of the clean coal before treatment is 2.5%, the average sulfur content of the clean coal after desulfurization is 1.2%, and the desulfurization rate is 52% under the above experimental conditions.
FIG. 1 is an infrared spectrogram before coal desulfurization, FIG. 2 is an infrared spectrogram after coal desulfurization by the method of the present invention, and absorption peaks of 744.62cm-1, 534.94cm-1, and 428.80cm-1 disappeared in FIG. 2 are organic sulfur-S-, -SH, A-S-A, thiophene, and FeS, that is, comparing FIG. 2 with FIG. 1, it can be seen that the sulfur content in coal is significantly reduced after coal desulfurization by the method.
Compared with the prior art, the invention has the advantages of low energy consumption, simple process and high sulfur content coal treatment, and the desulfurization rate can reach 40-55 percent after treatment.
The desulfurization and purification process of the oxidized coal by the electro-Fenton method has the obvious characteristics that the desulfurization and purification process is carried out at normal pressure and normal temperature; the desulfurization oxidant OH is generated in the reaction process, is easy to obtain and has low cost; the electrolysis process does not produce secondary pollution.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, the water addition amount, the coal-water slurry particle size, the hydrogen peroxide addition amount, and the FeSO defined in the above examples are not limited by the invention4·7H2Besides the experiment conditions of the solution addition amount of 0 and the limited PH range, the aim of desulfurization or cost reduction can be achieved through limited experiments, and the method also belongs to the protection range of the invention.
Claims (8)
1. A desulfurization method of oxidized coal by an electro-Fenton-iron reduction method is characterized by comprising the following steps:
the method comprises the following steps:
(1) adding water into coal in a certain proportion, and grinding the coal into coal water slurry with qualified particle size;
(2) mixing the coal water slurry obtained in the step (1) with FeSO4After the solutions are fully mixed, standing for 1-2 h, and mixing with hydrogen peroxide and acid liquor in a diaphragm-free electrolytic cell to form a Fenton reagent oxidation system;
(3) carrying out electrochemical reaction on the Fenton reagent oxidation system in the step (2) to obtain desulfurized coal water slurry;
(4) and (4) washing the desulfurized coal water slurry in the step (3) to be neutral, filtering and drying to obtain desulfurized coal powder.
2. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: in the step (1), water with a certain proportion is added according to the mass ratio of 50% +/-5% of coal.
3. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: the coal water slurry with qualified particle size in the step (1) is ground to prepare coal water slurry with particle size of 50-180 um.
4. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: the molar concentration of the hydrogen peroxide in the step (2) is 0.0546 mol/L-0.12 mol/L.
5. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, characterized in that: FeSO in step (2)4The solution is FeSO4·7H20 solution, FeSO4·7H20 is added in the amount of H in premix2O2Measured in a molar ratio of H2O2:Fe2+＝70:1～7。
6. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: and (3) in the step (2), the acid solution is sulfuric acid or hydrochloric acid, and the pH value of a mixed system of the Fenton reagent and the coal water slurry is adjusted to be 3 +/-0.5.
7. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: in the step (2), the diaphragm-free electrolytic cell and diaphragm-free electrolytic cell electrodes use stainless steel as cathodes and graphite as anodes, the distance between electrode plates of the cathodes and the anodes is 8-10 cm, two ends of the cathodes and the anodes are connected with a direct current power supply, and air is introduced below the electrolytic cell.
8. The method for desulfurizing an electro-Fenton-iron reduction-oxidized coal according to claim 1, wherein: in the step (3), the electrochemical reaction time is 3-5 h, the electrolytic voltage is 3-8V, the air flow is 1.5-2.5L/min, and the current density is 10-20 mA/cm3。
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| CN109650613A (en) * | 2019-02-25 | 2019-04-19 | 南京大学 | A kind of method of Split type electric Fenton equipment and its efficient process coal chemical industrial waste water |
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| CN115074164A (en) * | 2022-05-07 | 2022-09-20 | 塔里木大学 | Integrated cleaning and removing method for key harmful elements in hard-to-float bituminous coal |
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