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WO2020073813A1 - 一种固态碳质材料的除灰方法 - Google Patents

一种固态碳质材料的除灰方法 Download PDF

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Publication number
WO2020073813A1
WO2020073813A1 PCT/CN2019/108066 CN2019108066W WO2020073813A1 WO 2020073813 A1 WO2020073813 A1 WO 2020073813A1 CN 2019108066 W CN2019108066 W CN 2019108066W WO 2020073813 A1 WO2020073813 A1 WO 2020073813A1
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Prior art keywords
solid
alkali
coal
ash
carbonaceous material
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PCT/CN2019/108066
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English (en)
French (fr)
Inventor
赵利军
李文华
陈爱国
靳凡
姜晓琳
刘汇东
肖永丰
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Application filed by China Energy Investment Corp Ltd, National Institute of Clean and Low Carbon Energy filed Critical China Energy Investment Corp Ltd
Priority to KR1020217013629A priority Critical patent/KR102543116B1/ko
Priority to DE112019005110.5T priority patent/DE112019005110T5/de
Priority to JP2021516987A priority patent/JP7258128B2/ja
Priority to US17/284,594 priority patent/US12012334B2/en
Priority to AU2019357221A priority patent/AU2019357221B2/en
Publication of WO2020073813A1 publication Critical patent/WO2020073813A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/029—Salts, such as carbonates, oxides, hydroxides, percompounds, e.g. peroxides, perborates, nitrates, nitrites, sulfates, and silicates
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin

Definitions

  • the invention relates to the technical field of ash removal of solid carbonaceous materials, in particular to a ash removal method of solid carbonaceous materials.
  • Solid carbonaceous materials refer to solid materials rich in carbon, including solid fuels, activated carbon, asphalt, and other chemical materials.
  • Solid fuels refer to solid combustible materials that can generate heat or power. Most of them contain carbon or hydrocarbons. Natural Wood, peat, lignite, bituminous coal, anthracite, oil shale, etc. After processing, charcoal, coke, coal bricks, briquettes, etc. are obtained.
  • Solid carbonaceous materials usually contain ash. In application, the amount of ash content directly affects the performance of solid carbonaceous materials.
  • coal taking coal as an example, China's coal types are complex, the coal quality is generally poor, and the ash content is relatively high. After many years of mining, the coal quality has continued to decline.
  • the ash content of commercial coal is relatively high, with an average ash content of 20% to 24wt%, while the average ash content of coal for power generation reaches 28wt%.
  • the ash content of electric coal is reduced by 1wt%, the calorific value can be increased by 200-360J / g, and the standard coal consumption for power generation is reduced by 2-5g.
  • the ash content of coking coal is reduced by 1wt%, the consumption of iron-making coke is reduced by 2.66wt%, and the utilization factor of iron-making blast furnace can be increased by 3.99%. If synthetic anthracite is used in the production of synthetic ammonia, the coal can be saved by 20% by weight.
  • High value-added coal applications also include coal-based oil and coal-based carbon materials, which have strict limits on coal ash. As the "fuel coal water slurry" of coal substitute oil, the national standard stipulates that the ash content of grade I products is less than 6wt%. For coal-based carbon materials, it is recommended to use standard coal ash: activated carbon ⁇ 2wt%, carbon block and carbon electrode ⁇ 6wt%, electrode paste ⁇ 8wt%.
  • ultra-pure coal coal with ash content ⁇ 1-3wt% is also called ultra-pure coal.
  • the prepared fine coal water slurry is burned instead of oil, the boiler does not need to be reformed, the calorific value is high, and the environmental protection standard is met.
  • ultra-pure coal can also be used in power equipment such as internal combustion engines and gas turbines, as well as aviation turbine engines.
  • Chemical method is a method of chemical reaction through chemical agents and components in coal.
  • Physical methods mainly include oil agglomeration method and floc flotation method. Both use the difference in oleophilic and hydrophobic properties of organic matter and inorganic minerals in coal to refine raw coal.
  • the mill achieves monomer dissociation, and uses hydrocarbon and other neutral oil as bridging fluid and shearing force to agglomerate the oleophilic fine particles of organic matter, so that the hydrophilic mineral particles are dispersed and suspended in water, and then sieved, centrifuged or floated. Choose other methods to separate.
  • the physical method is relatively simple and easy to implement, but it has poor adaptability and low ash removal efficiency, while the chemical method has strong adaptability and high ash removal efficiency.
  • the chemical methods currently used mainly include hydrofluoric acid method, conventional acid-base method, molten alkali leaching method and chemical coal method.
  • the conventional acid-base method is the most widely used method.
  • the basic principle is that the alkali solution reacts with the minerals in the coal under certain conditions, and then the inorganic compounds formed by acid washing are removed, and the organic matter in the coal is separated by filtration and washing.
  • the method has strong adaptability and high ash removal efficiency.
  • the mass ratio of lye to coal can be as high as 3-10 or more.
  • the water consumption is large
  • the reaction conditions are harsh, the amount of alkali used is large, and the amount of coal processed is small, which increases the difficulty and cost of subsequent alkali recovery.
  • Embodiments of the present invention provide a method for removing ash from solid carbonaceous materials.
  • the reaction conditions are milder, and can remove ash more effectively, which can reduce the amount of alkali and water, increase the processing capacity of solid carbonaceous materials, and thus reduce the difficulty and cost of alkali recovery.
  • the present invention adopts the following technical solutions:
  • Embodiments of the present invention provide a method for removing ash from solid carbonaceous materials, including:
  • the acid solid is used to perform acid washing on the first solid product, and solid-liquid separation is performed again to obtain a second solid product and an acid washed liquid.
  • the mass ratio of the alkali to the solid carbonaceous material to be processed is between 0.1-2: 1.
  • the alkali sub-molten salt medium and the solid carbonaceous material to be treated are mixed under kneading.
  • the temperature of the reaction is 100-200 ° C
  • the pressure is normal pressure
  • the time is 0.5-9h.
  • the method for removing ash of the solid carbonaceous material further includes: cooling the mixed slurry after the reaction by a method of adding water for dilution.
  • the temperature after cooling is 10-99 ° C.
  • the cooling time is less than or equal to 3h.
  • the acid solution and the first solid product are n-pickled in countercurrent contact, wherein n is greater than or equal to 2.
  • the acid solution and the first solid product are subjected to n times of pickling treatment in a countercurrent contact manner, which specifically includes: using the pickling solution obtained by the i-th pickling treatment, to the i-1
  • the solid product obtained after the second pickling treatment is subjected to pickling treatment, and the pickling solution obtained after the second pickling treatment is used to perform pickling treatment on the first solid product, wherein, i is greater than or equal to 2 and less than Natural number equal to n.
  • the yield of the second solid product is greater than or equal to 95%.
  • the mass fraction of ash in the second solid product is less than or equal to 1%.
  • the mass fraction of ash in the second solid product is less than or equal to 0.2%.
  • Embodiments of the present invention provide a method for removing ash from solid carbonaceous materials.
  • alkali can be used to more effectively destroy or decompose mineral components, and then through acid pickling treatment, the damage can be eliminated. Or the decomposed mineral components are dissolved out to achieve the purpose of ash removal.
  • the vapor pressure generated by the sub-molten salt medium is less than atmospheric pressure and the reaction activity is high, the entire reaction process can be carried out under normal pressure.
  • the reaction conditions are milder and able to More effective ash removal can reduce the amount of alkali and water, increase the amount of solid carbonaceous materials, and reduce the difficulty and cost of alkali recovery.
  • FIG. 1 is a schematic flow chart of a method for removing ash from solid carbonaceous materials according to an embodiment of the present invention
  • FIG. 2 is a schematic flow chart of an acid pickling treatment performed by using an acid solution and a first solid product in countercurrent contact mode according to an embodiment of the present invention.
  • An embodiment of the present invention provides a method for removing ash from solid carbonaceous materials, referring to FIG. 1, including:
  • Ash in solid carbonaceous materials refers to the residues of solid carbonaceous materials after calcination. Solid carbonaceous materials undergo a series of physical and chemical changes at high temperatures. Organic components in them evaporate and escape, while inorganic components (inorganic salts and oxidation) Matter) is left behind, these residues are called ash.
  • Ash is divided into oxides or salts of various mineral elements. There are mainly Si, Al, Ca, Mg, K, Na, P, S, Fe, as well as lithium, gallium, uranium, mercury, rare earth and other rare elements and precious metals.
  • the sub-molten salt medium is sodium hydroxide or potassium hydroxide with a mass fraction greater than or equal to 50%.
  • the mass ratio of alkali to water may be 1: 1, 1.5: 1, 2: 1, 3: 1, or 4: 1.
  • the sub-molten salt medium is an alkali metal high-concentration ionization medium that can provide high activity negative oxygen ions. It is between the molten salt medium and the electrolyte solution medium. It has excellent physical and chemical properties such as low vapor pressure, high boiling point, and good fluidity, and High activity coefficient, high reactivity, adjustable separation function and other excellent reaction and separation characteristics can achieve efficient decomposition and conversion of mineral components. According to the above properties of sub-molten salts, in the present invention, the generated vapor pressure is less than atmospheric pressure, and a high activity reaction can be achieved under normal pressure.
  • Embodiments of the present invention provide a method for removing ash from solid carbonaceous materials.
  • alkali can be used to more effectively destroy or decompose mineral components, and then through acid pickling treatment, the damage can be eliminated. Or the decomposed mineral components are dissolved out to achieve the purpose of ash removal.
  • the vapor pressure generated by the sub-molten salt medium is less than atmospheric pressure and the reaction activity is high, the entire reaction process can be carried out under normal pressure.
  • the reaction conditions are milder and able to More effective ash removal can reduce the amount of alkali and water, increase the amount of solid carbonaceous materials, and reduce the difficulty and cost of alkali recovery.
  • the method before mixing the alkali sub-molten salt medium and the solid carbonaceous material to be processed, the method further includes: crushing the solid carbonaceous material to be processed to less than 5 mm, preferably less than 1 mm.
  • solid carbonaceous material is a broad concept, which can include: coal, coal direct liquefaction residue, heavy residue, coke, petroleum coke, oil sands, shale oil, carbonaceous industrial waste or tailings , Biomass, synthetic plastics, synthetic polymers, waste tires, municipal solid waste, asphalt and / or mixtures thereof.
  • the alkali coal ratio can be flexibly adjusted according to the different coal types and ash content.
  • a lower alkali coal ratio may be selected, such as 0.4: 1
  • a higher alkali coal ratio may be selected, such as 1.5: 1.
  • the mass ratio of the alkali to the solid carbonaceous material to be processed is between 0.1-2: 1.
  • the mass fraction of the alkali is greater than or equal to 50%.
  • the mass ratio of alkali to water may be 1: 1, 1.5: 1, 2: 1, 3: 1, or 4: 1. It can form sub-molten salt medium and improve ash removal efficiency.
  • the alkali sub-molten salt medium and the solid carbonaceous material to be treated are mixed under kneading.
  • the sub-molten salt medium is mixed with the solid carbonaceous material to be treated and the material is viscous at high temperature during the reaction. Kneading is the operation of uniformly mixing paste-like and viscous materials by mechanical agitation, usually using a pair of rotating ⁇ blades that cooperate with each other to produce a shearing effect, so that the semi-dry or rubber-like viscous materials react quickly to obtain a uniform Mix and stir. Compared with the usual mixing, it is more suitable for the mixing of high-viscosity materials, which makes the mixing of materials more uniform, thereby improving the ash removal efficiency, and can also reduce the material crushing phenomenon caused by stirring. If the material is too finely crushed, it will increase The cost of subsequent solid-liquid separation is not conducive to improving the yield of the product.
  • the temperature, pressure and time of the reaction are not specifically limited.
  • the reaction temperature is 100-200 ° C, preferably 105-150 ° C
  • the pressure is normal pressure
  • the time is 0.5-9h, preferably 2-6h.
  • atmospheric pressure is an atmospheric pressure, that is, the gas pressure generated by the atmosphere in which we normally live.
  • a standard atmospheric pressure is 101325Pa. Due to the difference in geographical location, altitude, temperature, etc. in each place, the actual atmospheric pressure in the area is not equal to the standard atmospheric pressure. However, the atmospheric pressure here can be approximated as a standard atmospheric pressure.
  • the temperature is reduced by 50-100 ° C compared with the conventional acid-base method
  • the pressure is normal pressure
  • the reaction conditions are mild
  • the ash removal efficiency is high
  • the reaction time can be shortened.
  • the obtained mixed slurry is viscous at high temperature, and if the solid-liquid separation is directly performed, the operation becomes more difficult. If the temperature is lowered before solid-liquid separation, the mixed slurry will condense into a solid with a certain hardness and strength, further increasing the difficulty of treatment. Therefore, preferably, before the solid-liquid separation of the mixed slurry after the reaction, the ash removal method further includes: cooling the mixed slurry after the reaction by a method of adding water for dilution.
  • the temperature of the mixed slurry after the reaction can be cooled to the extent that economic industrial separation can be performed, and on the other hand, after dilution with water, the mixed slurry can be maintained Flowable state to avoid solidification.
  • the temperature after cooling is not limited, as long as it is convenient to operate during solid-liquid separation.
  • the temperature after cooling is 10-99 ° C, preferably 30-60 ° C.
  • the temperature decrease time is less than or equal to 3h, and more preferably less than or equal to 1h. In this way, solid-liquid separation can be carried out on the materials after cooling down in time to avoid the instability of the system and precipitation, which affects the ash removal effect. If it can be handled in the future for some reason, it is necessary to break the cooling sediment first, or reheat the system to be viscous, and then add water to dilute it.
  • the temperature reduction time is less than or equal to 30 min.
  • the temperature reduction time is 10-15 min.
  • solid-liquid separation can be achieved by filtration.
  • the method further includes: washing the first solid product with water. It can wash away some alkali metal salts soluble in water.
  • the specific method of the acid washing treatment is not limited, and the acid liquid may be used to perform one or more acid washing treatments on the first solid product.
  • the acid solution and the first solid product are n-pickled in countercurrent contact, where n is a natural number greater than or equal to 2.
  • it includes: using the pickling solution obtained by the i-th pickling treatment, pickling the solid product obtained after the i-1 pickling treatment, and using the pickling solution obtained after the second pickling treatment Pickling the first solid product, wherein i is a natural number greater than or equal to 2 and less than or equal to n.
  • countercurrent contact can be used to pickle the solid product with the lowest ash content using the pickling solution with the lowest ash content.
  • the ash content in the pickling solution increases, the ash content increases gradually
  • the solid product is subjected to pickling treatment. Under a certain amount of acid solution, the pickling effect can be maximized and the ash content in the solid carbonaceous material can be further reduced.
  • the first solid product may be entered into a first pickling container, and the first solid product may be subjected to the first pickling treatment using the pickling liquid generated in the second pickling container To obtain the solid product and the pickling solution.
  • the solid product generated after the first pickling process enters the second pickling container.
  • the pickling solution from the third pickling container is used to enter the second pickling container.
  • the solid product is subjected to the second pickling treatment to obtain the solid product and the pickling solution again, and so on.
  • the solid product generated in the n-1 pickling container enters the nth pickling container, and the acid solution is used for the pickling treatment To obtain the second solid product and the pickling solution, and use the pickling solution obtained in the n-th pickling container to perform pickling treatment on the solid product entering the n-1 pickling container.
  • the first solid product is contacted with the acid solution in countercurrent step by step, which can further improve the ash removal effect.
  • the mass ratio of acid in the acid solution to the solid carbonaceous material to be treated is not limited, because after the alkali reacts with the mineral component in the solid carbonaceous material to be processed, the mineral component can be destroyed or decomposed, Through solid-liquid separation, very few mineral components enter the alkali treatment liquid. At this time, by adding acid solution to the first solid product for acid washing treatment, the destroyed or decomposed mineral components can be dissolved in the acid solution To enable ash removal. Therefore, the amount of acid added in the acid liquid can be flexibly adjusted according to the type and ash content of the solid carbonaceous material to be treated. Exemplarily, for a low-ash coal type, a lower acid-coal ratio may be selected, for example, 0.4: 1. For high-ash coal types, you can choose a higher acid-to-coal ratio, such as 1.5: 1.
  • the mass ratio of the acid in the acid solution to the solid carbonaceous material to be processed is between 0.1-2: 1.
  • the acid in the acid solution may be nitric acid, hydrochloric acid or sulfuric acid.
  • the mass fraction of the acid in the acid solution is not limited.
  • the mass fraction of acid in the acid solution is 3-30%. It is preferably 5-20%.
  • the method for removing ash of the solid carbonaceous material further includes: washing and drying the second solid product with water. The remaining acid in the second solid product is removed.
  • solid-liquid separation can be achieved by filtration.
  • the temperature and time of each pickling treatment are not specifically limited.
  • the temperature of each pickling treatment is 10-99 ° C. and the time is 5-180 min. If the temperature is too high or the pickling time is too long, the ash will be analyzed, which is not conducive to removal.
  • the yield of the second solid product can reach a high yield of more than 95-99%.
  • the mass fraction of ash in the second solid product is less than or equal to 1%. It can improve the performance of solid carbonaceous materials, such as coal can meet the requirements of ultra-pure coal, and improve the use value. When coal is used for combustion, the calorific value is greatly increased, and ash pollution to the environment is avoided.
  • the mass fraction of ash in the second solid product is less than or equal to 0.2%.
  • Recycling of water washing liquid and acid-base liquid can be carried out according to the existing mature technology.
  • the water washing liquid can be returned to step (1) for reuse after causticizing treatment, and the acid washing liquid can be recovered and reused by roasting and other methods.
  • M ad is the mass percentage of moisture
  • a ad is the mass percentage of ash
  • V ad is the mass percentage of volatile matter
  • FC ad is the mass percentage of fixed carbon.
  • the temperature of each pickling treatment is 99 °C, the time is 60 minutes, and filtration Washing and drying the filter cake yields the second solid product (ie ultrapure coal).
  • the yield of ultra-pure coal is 97.7%, and the ash content in ultra-pure coal is 0.43wt%.
  • the temperature of each acid washing treatment is 75 °C, the time is 5 minutes, filtration Wash and dry the filter cake to obtain the second solid product (ie ultrapure coal).
  • the yield of ultrapure coal is 98.0%, and the ash mass fraction in ultrapure coal is 0.78wt%.
  • the temperature of each pickling treatment is 20 °C, the time is 100 minutes, and the filtration Wash and dry the filter cake to obtain the second solid product (ie ultrapure coal).
  • the yield of ultrapure coal is 99.1%, and the mass fraction of ash in the ultrapure coal is 0.13wt%.
  • Example 1-6 kneading was used for the alkali coal reaction. Compared with the stirring in Comparative Examples 1-3, the pulverization of coal samples was reduced, the yield of ultra-pure coal was improved, and the ash removal effect was improved. Compared with the standing reaction in 7, kneading is more conducive to ash removal.

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Abstract

一种固态碳材料的除灰方法，属于固态碳质材料除灰技术领域，反应条件较为温和，且能够更有效地除灰，从而能够降低碱和水的用量，增大固态碳质材料的处理量，进而降低碱的回收难度和成本。所述除灰方法，包括：S1)将碱的亚熔盐介质和待处理固态碳质材料混合，加热，使得碱与所述待处理固态碳质材料中的灰分在所述碱的亚熔盐介质中发生反应，对反应后的混合浆液进行固液分离，获得第一固体产物和碱处理液，其中，在所述碱的亚熔盐介质中，所述碱的质量分数大于等于50％；S2)采用酸液对所述第一固体产物进行酸洗处理，并再次进行固液分离，获得第二固体产物和酸洗液。各实施例用于固态碳质材料除灰。

Description

一种固态碳质材料的除灰方法 技术领域
本发明涉及固态碳质材料除灰技术领域，尤其涉及一种固态碳质材料的除灰方法。
背景技术
固态碳质材料是指富含碳的固体材料，包括固体燃料、活性炭、沥青等化工材料等，固体燃料是指能够产生热能或动力的固态可燃物质，大都含有碳或碳氢化合物，天然的有木材、泥煤、褐煤、烟煤、无烟煤、油页岩等，经过加工获得的有木炭、焦炭、煤砖、煤球等。固态碳质材料中通常含有灰分，在应用时，灰分含量的多少直接影响到固态碳质材料的性能。
其中，以煤炭为例，中国煤炭种类复杂，煤质总体较差，灰分偏高，经过多年开采，煤质不断下降。商品煤灰分含量偏高，平均灰分在20％～24wt％，而发电用煤的平均灰分达到28wt％。在煤炭主要利用途径中，电煤灰分降低1wt％，发热量可提高200-360J/g，发电标准煤耗则下降2-5g。炼焦煤灰分降低1wt％，炼铁焦炭耗量降低2.66wt％，炼铁高炉利用系数可提高3.99％。合成氨生产如果使用洗选的无烟煤，可节煤20wt％。煤炭高附加值应用还包括煤代油和煤基炭材料，对煤炭的灰分都有严格限定。作为煤代油的“燃料水煤浆”，国家标准规定I级品灰分＜6wt％。对于煤基炭材料，推荐用煤标准灰分为：活性炭＜2wt％，炭块和炭电极＜6wt％，电极糊＜8wt％。一般把灰分＜1-3wt％的煤炭，又称为超纯煤，制备的精细水煤浆代油燃烧，锅炉无需改造，热值高，并且环保达标。此外，超纯煤还可用于内燃机和燃气轮机，以及航空涡轮发动机等动力设备。
对于煤炭精制，尤其是生产高附加值的精制低灰煤炭，主要有化学法和 物理法。化学法是通过化学药剂和煤中组分进行化学反应的方法，物理法主要有油团聚法和絮团浮选法，均利用煤中有机质和无机矿物亲油疏水性的差异，将原料煤细磨达到单体解离，借助烃类等中性油作桥连液和剪切力作用，将亲油细粒有机质团聚，使亲水矿物颗粒分散悬浮在水中，再通过筛分、离心或浮选等方式分离。物理法相对来说简单易行，但适应性差，除灰效率较低，而化学法适应性强、除灰效率高。目前所采用的化学法主要有氢氟酸法、常规酸碱法、熔融碱沥滤法和化学煤法。常规酸碱法是应用最广泛的方法，基本原理在于使碱溶液在一定条件下和煤中矿物进行反应，之后再用酸洗去形成的无机化合物，经过滤洗涤与煤中有机质分离，虽然此方法适应性强，除灰效率较高，但是，通常需要在150-250℃的高温高压下进行操作，同时碱液与煤炭的质量比可高达3-10以上，在整个过程中，用水量大，反应条件较为苛刻，且碱用量大，煤炭处理量小，加大了后续碱的回收难度与成本。
发明内容
本发明实施例提供一种固态碳质材料的除灰方法。反应条件较为温和，且能够更有效地除灰，从而能够降低碱和水的用量，增大固态碳质材料的处理量，进而降低碱的回收难度和成本。
为达到上述目的，本发明采用如下技术方案：
本发明实施例提供一种固态碳质材料的除灰方法，包括：
S1)将碱的亚熔盐介质和待处理固态碳质材料混合，加热，使得碱与所述待处理固态碳质材料中的矿物盐在所述碱的亚熔盐介质中发生反应，对反应后的混合浆液进行固液分离，获得第一固体产物和碱处理液，其中，在所述碱的亚熔盐介质中，所述碱的质量分数大于等于50％；
S2)采用酸液对所述第一固体产物进行酸洗处理，并再次进行固液分离，得到第二固体产物和酸洗液。
可选的，所述碱与所述待处理固态碳质材料的质量比介于0.1-2:1之间。
可选的，在捏合作用下将碱的亚熔盐介质和待处理固态碳质材料混合。
可选的，所述反应的温度为100-200℃，压力为常压，时间为0.5-9h。
可选的，对反应后的混合浆液进行固液分离之前，所述固态碳质材料的除灰方法还包括：采用加水稀释的方法对所述反应后的混合浆液进行降温。
可选的，所述降温后的温度为10-99℃。
可选的，所述降温的时间小于等于3h。
可选的，采用所述酸液与所述第一固体产物以逆流接触的方式进行n次酸洗处理，其中，n大于等于2。
可选的，采用所述酸液与所述第一固体产物以逆流接触的方式进行n次酸洗处理，具体包括：采用第i次酸洗处理所获得的酸洗液，对第i-1次酸洗处理后获得的固体产物进行酸洗处理，并且采用第二次酸洗处理后获得的酸洗液对所述第一固体产物进行酸洗处理，其中，所述i为大于等于2小于等于n的自然数。
可选的，所述第二固体产物的收率大于等于95％。
可选的，所述第二固体产物中灰分的质量分数小于等于1％。
可选的，所述第二固体产物中灰分的质量分数小于等于0.2％。
本发明实施例提供一种固态碳质材料的除灰方法，通过利用亚熔盐介质的高反应活性，能够使碱更有效地破坏或分解矿物组分，而后再通过酸洗处理，能够将破坏或分解后的矿物组分溶出，达到除灰的目的。由于亚熔盐介质所产生的蒸汽压小于大气压，且反应活性较高，因此，整个反应过程可以在常压下进行，与相关技术中所采用的酸碱法相比，反应条件较为温和，且能够更有效地除灰，从而能够降低碱和水的用量，增大固态碳质材料的处理量，进而降低碱的回收难度和成本。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中 所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例提供的一种固态碳质材料的除灰方法的流程示意图；
图2为本发明实施例提供的一种采用酸液与第一固体产物以逆流接触的方式进行n次酸洗处理的流程示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例提供一种固态碳质材料的除灰方法，参见图1，包括：
S1)将碱的亚熔盐介质和待处理固态碳质材料混合，加热，使得碱与该待处理固态碳质材料中的灰分在该碱的亚熔盐介质中发生反应，对反应后的混合浆液进行固液分离，获得第一固体产物和碱处理液，其中，在所述碱的亚熔盐介质中，所述碱的质量分数大于等于50％；
S2)采用酸液对第一固体产物进行酸洗处理，并再次进行固液分离，得到第二固体产物和酸洗液。
固态碳质材料中的灰分是指固态碳质材料煅烧后的残留物，固态碳质材料在高温下发生一系列物理和化学变化，其中的有机成分挥发逸散，而无机成分(无机盐和氧化物)被残留下来，这些残留物称为灰分。
灰分为各种矿物元素的氧化物或盐类。主要有Si、Al、Ca、Mg、K、Na、P、S、Fe，以及锂、镓、铀，汞，稀土等稀散元素和贵金属。
亚熔盐介质，是质量分数大于等于50％的氢氧化钠或氢氧化钾。示例性的，碱和水的质量比可以为1:1、1.5:1、2:1、3:1或4:1。亚熔盐介质是可提 供高活度负氧离子的碱金属高浓度离子化介质，介于熔盐介质和电解质溶液介质之间，具有蒸汽压低、沸点高、流动性好等优良物化性质，以及活度系数高、反应活性高、分离功能可调等优良反应和分离特性，可实现矿物组分的高效分解和转化。根据亚熔盐的以上性质，在本发明中，所产生的蒸汽压小于大气压，可在常压下实现高活性反应。
本发明实施例提供一种固态碳质材料的除灰方法，通过利用亚熔盐介质的高反应活性，能够使碱更有效地破坏或分解矿物组分，而后再通过酸洗处理，能够将破坏或分解后的矿物组分溶出，达到除灰的目的。由于亚熔盐介质所产生的蒸汽压小于大气压，且反应活性较高，因此，整个反应过程可以在常压下进行，与相关技术中所采用的酸碱法相比，反应条件较为温和，且能够更有效地除灰，从而能够降低碱和水的用量，增大固态碳质材料的处理量，进而降低碱的回收难度和成本。
其中，在将该碱的亚熔盐介质和待处理固态碳质材料混合之前，还包括：将该待处理固态碳质材料破碎至小于5mm，优选小于1mm。
其中，对该待处理固态碳质材料的种类和灰分含量不做限定，此方案适用于各种固态碳质材料除灰。在本说明书中，固态碳质材料是一个宽泛的概念，其可包括：煤、煤直接液化残渣、重质渣油、焦、石油焦、油砂、页岩油、碳质工业废料或尾料、生物质、合成塑料、合成聚合物、废轮胎、市政固体垃圾、沥青和/或它们的混合物。
以煤为例，根据煤种和灰分含量不同，可以对碱煤比进行灵活调整。
示例性的，对于低灰煤炭，可以选择较低的碱煤比，如0.4:1，对于高灰煤炭，可以选择较高的碱煤比，如1.5:1。
因此，可选的，碱与待处理固态碳质材料的质量比介于0.1-2:1之间。
本发明的一实施例中，在该碱的亚熔盐介质中，该碱的质量分数大于等于50％。示例性的，碱和水的质量比可以为1:1、1.5:1、2:1、3:1或4:1。能 够形成亚熔盐介质，提高除灰效率。
本发明的又一实施例中，在捏合作用下将碱的亚熔盐介质和待处理固态碳质材料混合。
亚熔盐介质与待处理固态碳质材料混合并在进行反应时，物料呈高温粘稠状。捏合是利用机械搅拌使糊状、黏性物料均匀混合的操作，通常采用一对互相配合的旋转Σ桨叶产生剪切作用，从而使半干状态或橡胶状粘稠材料迅速反应从而获得均匀的混合搅拌。与通常所说搅拌相比，更适合于高粘度物料的混合，使得物料混合更加均匀，从而提高除灰效率，并且，还能够减少搅拌所带来的物料粉碎现象，若物料过于细碎，会增加后续固液分离的成本，且不利于提高产物的收率。
其中，对该反应的温度、压力和时间均不做具体限定。本发明的一实施例中，该反应温度为100-200℃，优选为105-150℃，压力为常压，时间0.5-9h，优选为2-6h。
其中，常压即一个大气压，也就是我们平常生活的这个大气层产生的气体压力。一个标准大气压为101325Pa。每个地方由于地理位置、海拔高度、温度等不同，当地的实际大气压跟标准大气压也不相等，仅此，这里的常压可以近似认为是一个标准大气压。
在本发明实施例中，温度与常规酸碱法相比降低50-100℃，压力为常压，反应条件温和，除灰效率较高，能够缩短反应时间。
其中，需要说明的是，在实际应用中，在步骤S1)完成之后，所获得的混合浆液呈高温粘稠状，若直接进行固液分离则操作难度加大。而若在对其进行固液分离之前进行降温处理，则混合浆液将会凝结成具有一定硬度和强度的固体，进一步加大处理难度。因此，优选的，在对反应后的混合浆液进行固液分离之前，所述除灰方法还包括：采用加水稀释的方法对该反应后的混合浆液进行降温。这样一来，通过对反应后的混合浆液进行稀释，一方 面能够对反应后的混合浆液进行降温，达到可进行经济的工业分离的程度，另一方面在加水稀释后，可以让混合浆液能够保持可流动状态，避免凝结成固体。
其中，对降温后温度不做限定，只要在固液分离时方便操作即可。本发明的一实施例中，降温后的温度为10-99℃，优选为30-60℃。
其中，还需要说明的是，在实际应用中，在将反应后的混合浆液降温至10-99℃后，体系呈亚稳状态，若长时间放置会引起可溶于水的碱金属盐的析出，因此，优选的，该降温的时间小于等于3h，更优选小于等于1h。这样一来，能够对降温后的物料及时进行固液分离，避免体系失稳而析出沉淀，影响除灰效果。如果因故未来得及处理，需要先对降温沉淀破碎，或者把体系重新加热粘稠，再加水稀释。
进一步优选的，该降温的时间小于等于30min。
更进一步地，该降温的时间为10-15min。
其中，可以采用过滤的方式实现固液分离。
本发明的又一实施例中，在固液分离后，在采用酸液对第一固体产物进行酸洗处理之前，该方法还包括：用水对第一固体产物进行洗涤。能够洗掉可溶于水的部分碱金属盐。
其中，对该酸洗处理的具体方式不做限定，可以采用该酸液对该第一固体产物进行一次或多次酸洗处理。
本发明的一实施例中，采用该酸液与该第一固体产物以逆流接触的方式进行n次酸洗处理，其中，n为大于等于2的自然数。
具体包括：采用第i次酸洗处理所获得的酸洗液，对第i-1次酸洗处理后获得的固体产物进行酸洗处理，并且采用第二次酸洗处理后获得的酸洗液对所述第一固体产物进行酸洗处理，其中，所述i为大于等于2小于等于n的自然数。
在本发明实施例中，采用逆流接触，能够采用灰分含量最低的酸洗液对灰分含量最低的固体产物进行酸洗处理，随着酸洗液中灰分含量越高，依次对灰分含量逐渐增高的固体产物进行酸洗处理，在酸液的用量一定的情况下，能够最大程度上提高酸洗效果，进一步降低固态碳质材料中的灰分含量。
在实际应用中，参见图2，可以将该第一固体产物进入第一酸洗容器中，采用来自第二酸洗容器中产生的酸洗液对该第一固体产物进行第一次酸洗处理，获得固体产物和酸洗液，第一次酸洗处理后产生的固体产物进入第二酸洗容器中，采用来自第三酸洗容器中产生的酸洗液对进入第二酸洗容器中的固体产物进行第二次酸洗处理，再次获得固体产物和酸洗液，依次类推，第n-1酸洗容器中产生的固体产物进入第n酸洗容器中，采用该酸液进行酸洗处理，获得第二固体产物和酸洗液，采用第n酸洗容器中获得的酸洗液对进入第n-1酸洗容器中的固体产物进行酸洗处理。
以上过程中，第一固体产物与酸液逐级逆流接触，能够进一步提高除灰效果。
其中，对酸液中酸与待处理固态碳质材料的质量比不做限定，由于在碱与待处理固态碳质材料中的矿物组分发生反应之后，能够将矿物组分破坏或分解掉，通过固液分离，极少的矿物组分进入碱处理液中，这时，通过加入酸液对第一固体产物进行酸洗处理，能够将被破坏或分解掉的矿物组分溶解于酸液中，得以进行除灰。因此，酸液中酸的加入量可以根据待处理固态碳质材料的种类和灰分含量进行灵活调整，示例性的，对于低灰煤种，可以选择较低的酸煤比，例如0.4:1。对于高灰煤种，可以选择较高的酸煤比，例如1.5:1。
因此，可选的，该酸液中酸与待处理固态碳质材料的质量比介于0.1-2:1之间。
其中，该酸液中酸可以为硝酸、盐酸或硫酸。
其中，对该酸液中酸的质量分数不做限定。
本发明的一实施例中，该酸液中酸的质量分数为3-30％。优选为5-20％。
其中，在再次进行固液分离获得第二固体产物和酸洗液的过程中，该固态碳质材料的除灰方法还包括：用水对第二固体产物进行洗涤干燥。去除第二固体产物中残留的酸液。
其中，可以采用过滤的方式实现固液分离。
其中，对每一次该酸洗处理的温度和时间均不做具体限定。
本发明的又一实施例中，每一次该酸洗处理的温度为10-99℃，时间为5-180min。温度过高或酸洗时间过长都会使灰分析出，不利于去除。
经过试验发现，采用该除灰方法，该第二固体产物的收率可以达到95-99％以上的高收率。该第二固体产物中灰分的质量分数小于等于1％。能够提高固态碳质材料的性能，如煤炭能够达到超纯煤要求，提高了利用价值。在将煤炭用于燃烧时，大大提高了发热量，避免灰分对环境造成污染。
优选的，该第二固体产物中灰分的质量分数小于等于0.2％。
对于水洗液和酸碱液的回收利用，可按照现有的成熟技术进行。例如，水洗液可以在苛化处理后返回步骤(1)进行回用，酸洗液可以通过焙烧等方式，对酸进行回收和再利用。
以下，本发明实施例将通过对比例和实施例对本发明进行详细说明。这些对比例和实施例仅是为了具体说明本发明而提出的示例，本领域技术人员可以知道的是本发明的范围不受这些对比例和实施例的限制。
对于煤样A和煤样B，工业分析结果如下表1。
表1
煤样 M ad A ad V ad FC ad
A 6.30 34.25 24.63 34.82
B 2.33 5.12 20.57 71.98
其中，M ad是水分的质量百分含量，A ad是灰分的质量百分含量，V ad是挥发分的质量百分含量，FC ad是固定碳的质量百分含量。煤样均破碎至小于5mm，且部分小于1mm。
实施例1
取煤样A 400g，与氢氧化钠700g和水400ml(氢氧化钠的质量分数为63.6％，碱煤比为7:4，碱液与煤样A的质量比为11:4)，混合后在105℃、密闭环境中，常压下捏合反应9小时。加1L水稀释降温，1小时后过滤洗涤，获得第一固体产物(即碱煤)。按酸煤比1.3:1在碱煤中加入10wt％稀盐酸，对碱煤进行酸洗处理，温度为60℃，时间为30分钟，过滤洗涤并对滤饼进行干燥，获得第二固体产物(即超纯煤)。超纯煤的收率为97.1％，超纯煤中灰分的质量分数为0.35wt％。
实施例2
取煤样A 400g，与氢氧化钠600g和水300ml(氢氧化钠的质量分数为66.7％，碱煤比为3:2，碱液与煤样A的质量比为9:4)，混合后在150℃、密闭环境中，常压下捏合反应5小时。加1L水稀释降温，30分钟后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比1.1:1在碱煤中加入20wt％稀硫酸，对碱煤进行3次酸洗处理，每一次酸洗处理的温度为99℃，时间为60分钟，过滤洗涤并对滤饼干燥获得第二固体产物(即超纯煤)。超纯煤收率为97.7％，超纯煤中灰分质量分数为0.43wt％。
实施例3
取煤样A 400g，与氢氧化钾600g和水200ml(氢氧化钾的质量分数为75％，碱煤比为3:2，碱液与煤样A的质量比为8:4)，混合后在175℃、密闭环境中，常压下捏合反应2小时。加1L水稀释降温，15分钟后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比0.9:1在碱煤中加入15wt％稀硝酸，对碱煤进行4次酸洗处理，每一次酸洗处理的温度为 75℃，时间为5分钟，过滤洗涤并对滤饼进行干燥获得第二固体产物(即超纯煤)。超纯煤的收率为98.0％，超纯煤中灰分质量分数为0.78wt％。
实施例4
取煤样B 400g，与氢氧化钠160g和水100ml(氢氧化钠的质量分数为61.5％，碱煤比为0.4:1，碱液与煤样B的质量比为2.6:4)，混合后在120℃、密闭环境中，常压下捏合反应6小时。加1L水稀释降温，30分钟后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比0.4:1在碱煤中加入10wt％稀盐酸，对碱煤进行5次酸洗处理，每一次酸洗处理的温度为20℃，时间为100分钟，过滤洗涤并对滤饼进行干燥获得第二固体产物(即超纯煤)。超纯煤的收率为99.1％，超纯煤中灰分的质量分数为0.13wt％。
实施例5
取煤样B 400g，与氢氧化钠40g和水40ml(氢氧化钠的质量分数为50％，碱煤比为0.1:1，碱液与煤样B的质量比为0.8:4)，混合后在密闭环境中，200℃下捏合反应0.5小时。加1L水稀释降温，30分钟后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比0.4:1在碱煤中加入10wt％稀盐酸，对碱煤进行3次酸洗处理，每一次酸洗处理的温度为10℃，时间为180分钟，过滤洗涤并对滤饼进行干燥获得第二固体产物(即超纯煤)。超纯煤的收率为99.3％，超纯煤中灰分的质量分数为0.28wt％。
实施例6
取煤样A 400g，与氢氧化钠700g和水400ml(氢氧化钠的质量分数为63.6％，碱煤比为7:4，碱液与煤样A的质量比为11:4)，混合后在密闭环境中，100℃下捏合反应9小时。加1L水稀释降温，1小时后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比1.3:1加入10wt％稀盐酸，对碱煤进行3次酸洗处理，每一次酸洗处理的温度为99℃，时间为30分钟，过滤洗涤并对滤饼进行干燥获得第二固体产物(即超纯煤)，超纯 煤收率为97.2％，超纯煤中灰分质量分数为0.12wt％。
实施例7
取煤样A 400g，与氢氧化钠700g和水400ml(氢氧化钠的质量分数为63.6％，碱煤比为7:4，碱液与煤样A的质量比为11:4)，混合后在密闭环境中，100℃下静置，反应9小时。加1L水稀释降温，1小时后过滤洗涤，获得第一固体产物(即碱煤)。以逆流接触的方式，按酸煤比1.3:1加入10wt％稀盐酸，对碱煤进行3次酸洗处理，每一次酸洗处理的温度为99℃，时间为30分钟，过滤洗涤并对滤饼进行干燥获得第二固体产物(即超纯煤)，超纯煤收率为97.1％，超纯煤中灰分质量分数为0.98wt％。
对比例1
取煤样A 100g，与氢氧化钠200g和水800ml(氢氧化钠的质量分数为20％，碱煤比为2:1，碱液与煤样A的质量比为10:1)，混合后在250℃、对应饱和蒸汽压下(约40个大气压)搅拌反应6小时。过滤洗涤后获得碱煤，按酸煤比1.3:1在碱煤中加入10wt％稀盐酸，60℃下浸出30分钟，过滤洗涤并对滤饼进行干燥获得超纯煤。超纯煤的收率为57.9wt％，超纯煤中灰分的质量分数为5.67wt％。
对比例2
取煤样A 100g，与氢氧化钠400g和水600ml(氢氧化钠的质量分数为40％，碱煤比为4:1，碱液与煤样A的质量比为10:1)，混合后在250℃、对应饱和蒸汽压下(约40个大气压)搅拌反应6小时。过滤洗涤后获得碱煤，按酸煤比1.3:1在碱煤中加入10wt％稀盐酸，60℃下浸出30分钟，过滤洗涤并对滤饼进行干燥获得超纯煤。超纯煤的收率为65.1wt％，超纯煤中灰分的质量分数为3.53wt％。
对比例3
取煤样B 100g，与氢氧化钠80g和水320ml(氢氧化钠的质量分数为20％， 碱煤比为4:5，碱液与煤样B的质量比为4:1)，混合后在220℃、对应饱和蒸汽压下(约20个大气压)搅拌反应6小时。过滤洗涤后获得碱煤，按酸煤比0.4:1在碱煤中加入10wt％稀盐酸，75℃下浸出30分钟，过滤洗涤并对滤饼进行干燥获得超纯煤。超纯煤的收率为79.7％，超纯煤中灰分的质量分数为1.39wt％。
由以上实施例1-6和对比例1-3可见，对于高灰煤样A和低灰煤样B，碱质量分数大于等于50％，可常压反应，活性增强，碱添加量可减少一倍以上并减少用水，碱煤反应温度可降低50-100℃，而最终所获得的超纯煤收率较高，灰分含量显著降低。由实施例6与实施例1比较可知，采用多级逆流接触的方式对碱煤进行酸洗处理，能够更进一步提高灰分去除效果，所获得的超纯煤灰分质量分数可达到0.2％以下。此外，在实施例1-6中，碱煤反应采用捏合，与对比例1-3中的搅拌相比，煤样粉碎减少，超纯煤得率提高，并改善了灰分去除效果，与实施例7中静置反应相比，捏合更有利于灰分去除。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (12)

  1. 一种固态碳质材料的除灰方法，其特征在于，包括：
    S1)将碱的亚熔盐介质和待处理固态碳质材料混合，加热，使得碱与所述待处理固态碳质材料中的灰分在所述碱的亚熔盐介质中发生反应，对反应后的混合浆液进行固液分离，获得第一固体产物和碱处理液，其中，在所述碱的亚熔盐介质中，所述碱的质量分数大于等于50％；
    S2)采用酸液对所述第一固体产物进行酸洗处理，并再次进行固液分离，获得第二固体产物和酸洗液。
  2. 根据权利要求1所述的固态碳质材料的除灰方法，其特征在于，所述碱与所述待处理固态碳质材料的质量比介于0.1-2:1之间。
  3. 根据权利要求1所述的固态碳质材料的除灰方法，其特征在于，在捏合作用下将碱的亚熔盐介质和待处理固态碳质材料混合。
  4. 根据权利要求1所述的固态碳质材料的除灰方法，其特征在于，所述反应的温度为100-200℃，压力为常压，时间为0.5-9h。
  5. 根据权利要求1-4中任一项所述的固态碳质材料的除灰方法，其特征在于，对反应后的混合浆液进行固液分离之前，所述除灰方法还包括：采用加水稀释的方法对所述反应后的混合浆液进行降温。
  6. 根据权利要求5所述的固态碳质材料的除灰方法，其特征在于，所述降温后的温度为10-99℃。
  7. 根据权利要求6所述的固态碳质材料的除灰方法，其特征在于，所述降温的时间小于等于3h。
  8. 根据权利要求1所述的固态碳质材料的除灰方法，其特征在于，采用所述酸液与所述第一固体产物以逆流接触的方式进行n次酸洗处理，其中，n大于等于2。
  9. 根据权利要求8所述的固态碳质材料的除灰方法，其特征在于，采用所述酸液与所述第一固体产物以逆流接触的方式进行n次酸洗处理，具体包括：
    采用第i次酸洗处理所获得的酸洗液，对第i-1次酸洗处理后获得的固体产物进行酸洗处理，并且采用第二次酸洗处理后获得的酸洗液对所述第一固体产物进行酸洗处理，其中，所述i为大于等于2小于等于n的自然数。
  10. 根据权利要求1所述的固态碳质材料的除灰方法，其特征在于，所述第二固体产物的收率大于等于95％。
  11. 根据权利要求1或10所述的固态碳质材料的除灰方法，其特征在于，所述第二固体产物中灰分的质量分数小于等于1％。
  12. 根据权利要求11所述的固态碳质材料的除灰方法，其特征在于，所述第二固体产物中灰分的质量分数小于等于0.2％。
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