CN110003965A - A kind of method that ball milling pretreatment-chemical method joint prepares ultra-fine Filter Tuber For Clean Coal - Google Patents
A kind of method that ball milling pretreatment-chemical method joint prepares ultra-fine Filter Tuber For Clean Coal Download PDFInfo
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- CN110003965A CN110003965A CN201910384240.9A CN201910384240A CN110003965A CN 110003965 A CN110003965 A CN 110003965A CN 201910384240 A CN201910384240 A CN 201910384240A CN 110003965 A CN110003965 A CN 110003965A
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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
- 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
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
- C10L9/083—Torrefaction
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/08—Drying or removing water
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/22—Impregnation or immersion of a fuel component or a fuel as a whole
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/28—Cutting, disintegrating, shredding or grinding
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
- C10L2290/547—Filtration for separating fractions, components or impurities during preparation or upgrading of a fuel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a kind of ball milling pretreatment-chemical methods to combine the method for preparing ultra-fine Filter Tuber For Clean Coal, includes the following steps: to obtain coal particle after roasting in protective atmosphere after anthracite is crushed by (1)；Dispersing agent is added into resulting coal particle, control abrading-ball gradation is drying to obtain microfine coal after carrying out ball milling；(2) it after mixing microfine coal with surfactant, is added in the mixing immersion liquid of acid and fluoride salt, is filtered, washed after heated leaching, is drying to obtain ultra-fine clean anchracite duff.The present invention by broken anthracite in protective atmosphere devolatilization, cooperate with ball milling pretreatment, the microfine coal that available partial size is small and distributed area is narrow, then after cleaning, gained microfine coal purity is not less than 99.5wt%.
Description
Technical field
The present invention relates to a kind of ball milling pretreatment-chemical methods to combine the method for preparing ultra-fine Filter Tuber For Clean Coal, belongs to function carbon dust
Body technical field of material.
Technical background
Filter Tuber For Clean Coal is a kind of coal product of high added value, can be used as exotic fuels diesel oil substitute and natural gas for interior
Combustion engine, gas turbine, aero-turbine etc., such as the abrasion for reducing pump, nozzle, piston and turbine wheel and deslagging shadow
It rings, automotive fuel generally requires ultrapure pit ash below 1.0%；On the other hand, Filter Tuber For Clean Coal can also be used for preparing high-quality
High performance carbon cellulosic material, such as carbon fibre composite, graphite electrode, new energy materials field etc..Therefore, Filter Tuber For Clean Coal
Preparation is coal retrofit and the inexorable trend for improving added value, and carries out grinding for mineral disaggregation and Filter Tuber For Clean Coal technology of preparing
Study carefully, obtains a kind of novel high-energy fuel and high-quality carbon materials, have broad application prospects and potential tremendous economic society
It can benefit.New energy materials are produced as emerging industry as country continued to increase New Energy Industry support policy in recent years
Industry has welcome the growth of explosion type.Energy storage and conversion equipment determine the key of New Energy Industry, and energy storage and
The key of conversion equipment is material.Cell negative electrode material be usually be made of carbon material, for new energy materials for
The granularity of material and purity requirement are very harsh.Coal reserves is abundant, phosphorus content is high, cheap, is current research and development and preparation
The important source material of new energy materials.But the defect due to coal inherently, it generally cannot directly use, need to carry out it
Edulcoration purification makes its purity reach 99.5% or more, while the granularity requirements of coal are less than 30um.
Patent CN103537355A discloses the preparation system and method for a kind of microfine coal, utilizes fine powder pulverized coal preparation system
With superfine powder separation system, realizes the preparation of fine powder, the separation of superfine powder and extract two parts.Superfine powder is through grader, rotation
Wind separator and the separation of pulse bag dust-precipitator three-level and extraction obtain different grades of microfine coal.But fine Coal in the program
Powder is the product obtained by screening separation, is not full constituent microfine coal, and the program is only primary grinding, microfine coal
Middle coarse granule accounting is big.
Patent CN107626438A discloses a kind of technique that super clean coal is prepared using anthracite physical method, including following step
Rapid: 200 mesh of mistake that anthracite is levigate obtains coal sample and carries out float test to coal sample, obtains floatation clean coal.It is added in floatation clean coal
Sodium metasilicate carries out substep release and obtains substep release cleaned coal.It pours into spiral chute after mixing evenly, obtains spiral separating essence
Coal；Wherein, the chats obtained after Jing Yici spiral separating should return spiral chute again spiral separating in spiral separating cleaned coal
Kerosene is added in middle addition sodium metasilicate and water, stirring a period of time, continues stirring a period of time, dries after sieving, oversize is
Super clean coal.It obtains ultrapure coal particle slightly and impurity content is higher (content of ashes < 2%).
Patent CN107674725A discloses a kind of technique that super clean coal is prepared using anthracite chemistry method, including following step
It is rapid: 1) to take anthracite, levigate 200 mesh of mistake obtains coal sample；2) NaOH is added into coal sample, in 200 DEG C of roasting 12h, filters,
Obtain a dant；3) 5%HCl is added into a dant, 1h is stirred at room temperature, filtering drying obtains super clean coal.The patent can only
Super clean coal of the content of ashes less than 2% is obtained, content of ashes is relatively high, and the partial size of the super clean coal of acquisition is not able to satisfy function slightly
Requirement of the toner body material to partial size and purity.
Patent CN107892971A discloses a kind of technique that super clean coal is prepared using anthracite physical-chemical method, including
Following steps: 1) taking anthracite, levigate to cross 0.5mm sieve, obtains coal sample；2) float test is carried out to coal sample, obtains floatation clean coal；
3) NaOH is added into floatation clean coal, in 200 DEG C of roasting 12h, filtering obtains two dants；4) 5%HCl into two dants, in room
Temperature stirring 1h, filtering drying obtain super clean coal.The patent can only obtain super clean coal of the content of ashes less than 2%, content of ashes phase
To higher, the very thick requirement for not being able to satisfy functional carbon powder body material of the partial size of the super clean coal of acquisition.
Patent CN105728156A discloses a kind of preparation process of super clean coal, makes suitable for minerals separation technical field
With.One low ash anthracite is entered in tertiary industry product interference bed after efficient fine crusher is broken and is sorted, obtain coarse-fine coal, in
Coal, spoil；Coarse-fine coal obtains the ultrapure product of coal of coarse grain after coal slime centrifuge dehydration through three-product cyclone sieve classification；Middle coal is through one
After secondary corase grinding enter sieve bend be classified, sieve bend sieve on enter spiral throw tail, after the secondary fine grinding of light product with three products
Enter floatation equipment flotation together under vortex sieve sieve, under overflow, coal slime centrifuge centrifugate and sieve bend sieve, it is super to obtain particulate
Pure product of coal.
It is more about the broken technique for preparing duff of anthracite, fail to be able to satisfy to novel carbon material mostly to partial size
It is required that simultaneously for for the preparation of ashless coal although method is more finally obtained ash content of coal content it is higher (content of ashes >
1.0%) to find out its cause, these techniques there is at least one drawbacks, not such as complex process, equipment seriously corroded, valuable material
It can effectively recycle, processing cost is high, environmental protection pressure is big, energy consumption is high, and impurity content is higher etc..For new energy materials field,
Current impurity removal process and crushing process is far from satisfying requirement of the new energy negative electrode material to impurity content and partial size, causes
Its technique does not obtain industrial application.
Summary of the invention
For the technical problem that content of ashes is high and coal particle size is excessive after the removal of impurities of existing coal dust, the purpose of the present invention is
In providing a kind of method that ball milling pretreatment-chemical method joint prepares ultra-fine Filter Tuber For Clean Coal, by existing to broken anthracite
Devolatilization in protective atmosphere, collaboration ball milling pretreatment, the microfine coal that available partial size is small and distributed area is narrow, then
After cleaning, gained microfine coal purity is not less than 99.5wt%.
In order to achieve the above technical purposes, the present invention adopts the following technical scheme:
A kind of method that ball milling pretreatment-chemical method joint prepares ultra-fine Filter Tuber For Clean Coal, includes the following steps:
(1) coal particle is obtained after roasting in protective atmosphere after being crushed anthracite；It is added into resulting coal particle
Dispersing agent, control abrading-ball gradation are drying to obtain microfine coal after carrying out ball milling；
(2) it after mixing microfine coal with surfactant, is added in the mixing immersion liquid of acid and fluoride salt, heated leaching
It is filtered, washed after out, is drying to obtain ultra-fine clean coal dust.
Containing a large amount of aliphatic hydrocarbon, aromatic hydrocarbon, containing organic matters such as oxynitrides and heterocyclic compounds in coal, lead to coal
With viscosity, inventor has found that this viscosity can hinder the thinning process of coal, is being crushed to using conventional mechanical crushing process
It cannot continue refinement after certain particle size, or even agglomeration can occur.The present invention by broken anthracite into
The roasting of row protective atmosphere effectively removes the partial organic substances in coal, reduces the viscosity of coal dust, Collaborative Control ball milling pretreatment work
Skill parameter, the microfine coal that available partial size is small and distributed area is narrow.
Preferably, in step (1), anthracite is crushed to -200 mesh.
Preferably, in step (1), the protective atmosphere is at least one of nitrogen, helium, argon gas.
Preferably, in step (1), the maturing temperature is 400-800 DEG C, time 2-8h.
Preferably, in step (1), the dispersing agent is triethanolamine, in alkyl enuatrol, polyethylene glycol, ethyl alcohol
At least one, additive amount are 1-100mL/300g coal particle.
Preferably, in step (1), the abrading-ball be stainless steel, hard alloy, polyurethane, zirconium oxide, in agate at least
One kind, gradation are that the quantity of big ball, middle ball and bead than the quantity ratio for 1:1-3:1-6 or middle ball and bead is 1:1-2.
Preferably, in step (1), ball material mass ratio when ball milling is 5-20:1, rotational speed of ball-mill 200-500r/min, ball
Time consuming is 6-12h.
Preferably, in step (1), the drying mode is vacuum drying, and temperature is 70~90 DEG C or freeze-drying, temperature
Degree is -10~-50 DEG C.Microfine coal after mechanical activation has the characteristics that large specific surface area, activity are good, using of the invention preferred
Drying mode, can prevent as far as possible it is destructurized, keep microfine coal activity.
Preferably, in step (2), surfactant is in ethyl alcohol, polyethylene glycol, triethanolamine and alkyl enuatrol
At least one, preferably ethyl alcohol；Dosage of surfactant is the 2-15wt% of microfine coal quality, preferably microfine coal quality
10wt%.
Preferably, in step (2), acid is selected from least one of nitric acid, hydrochloric acid, preferably hydrochloric acid；Acid concentration is 2.0-
8.0mol/L, preferably acid concentration are 6.0mol/L；Fluoride salt in sodium fluoride, aluminum fluoride, lithium fluoride, calcirm-fluoride at least one
Kind, preferably sodium fluoride；Fluorination salinity is 5-30g/L, preferably 18g/L.
Preferably, in step (2), the liquid-solid ratio for mixing immersion liquid and microfine coal is 5-30mL/g, and preferably liquid-solid ratio is
15mL/g；Heating extraction temperature is 40-90 DEG C, preferably 60 DEG C；Heating extraction time is 1-5h, preferably 2h.
The invention has the following advantages:
1, the present invention is by the way that broken anthracite, devolatilization, Collaborative Control ball milling are located in advance in protective atmosphere
Technological parameter is managed, has broken the refinement bottleneck problem in tradition machinery disintegrating process, available partial size is smaller and distributed area
Narrow microfine coal, 3 μm of coal particle size D90 < promote subsequent removal of impurities so that the impurity wrapped up in coal is sufficiently exposed
Technique.
2, the present invention cleans to pretreated microfine coal using acid+fluoride salt mixing immersion liquid, and acid can remove in coal
Metal oxide, metal carbonate and acid soluble impurity, and joined fluoride salt in acid condition can remove difficulty
The inorganic salt impurities that hydrofluoric acid is reacted but dissolved in hydrochloric acid, further improve impurity-eliminating effect.
3, the present invention is by the way that broken anthracite, devolatilization, Collaborative Control ball milling are located in advance in protective atmosphere
Technological parameter is managed, obtains the microfine coal that partial size is smaller and distributed area is narrow, then using acid+fluoride salt mixing immersion liquid removal of impurities, it is real
The ultra high efficiency removal for having showed various impurity in anthracite can get the ultra-fine clean anthracite of content of ashes < 0.5wt%, can be with
Fully meet requirement of the new energy negative electrode material to purity and partial size.The present invention is under the synergistic effect of each processing step, institute
It obtains ultra-fine anchracite duff purity and is not less than 99.5wt%.
Detailed description of the invention
Fig. 1 is the grain size distribution of microfine coal made from embodiment 1；
Fig. 2 is the grain size distribution of microfine coal made from embodiment 2；
Fig. 3 is the grain size distribution of microfine coal made from embodiment 3；
Fig. 4 is the grain size distribution of microfine coal made from comparative example 1；
Fig. 5 is the grain size distribution of microfine coal made from comparative example 2.
Specific embodiment
It is described further combined with specific embodiments below, but the present invention is not therefore subject to any restriction.
The anthracite component mass content used in various embodiments of the present invention and comparative example are as follows: fixing carbon content is
86.24%, volatilization is divided into 9.32%, content of ashes 3.4%, moisture content 1.04%.Ash content essential element mass content
Are as follows: O29.48, Si20.00, Al15.58, Fe11.21, Ca11.02, S4.49, Mg2.70, Na2.66.
Embodiment 1
It takes anthracite to be tentatively crushed to -200 mesh, is placed in corundum crucible, 600 DEG C of heat preservations in nitrogen atmosphere in Muffle furnace
8h, devolatilization.
Coal dust 50g after taking devolatilization, is added in zirconia ball grinding jar, and 10ml dehydrated alcohol is added in ball grinder, is situated between
Matter ball selective oxidation zirconium ball, control medium ball gradation are middle ball: bead=1:1, ratio of grinding media to material=10:1, planetary ball mill revolving speed
300r/min, Ball-milling Time 12h obtain the microfine coal of favorable dispersibility, through laser particle size in vacuum oven after dry 4h
Tester measures the particle diameter distribution of coal dust, as shown in Figure 1, D50=0.855 μm, D90=1.609 μm.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added to the mixing immersion liquid of hydrochloric acid and sodium fluoride
Middle removal of impurities, wherein concentration of hydrochloric acid is 6.0mol/L, and NaF concentration is 18g/L, and acidleach temperature is 60 DEG C, time 2h, and liquid-solid ratio is
15mL/g is filtered after acidleach, is washed to neutrality, and filter residue dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 99.86%.
Embodiment 2
It takes anthracite to be tentatively crushed to -200 mesh, is placed in corundum crucible, 650 DEG C of heat preservations in nitrogen atmosphere in Muffle furnace
4h, devolatilization.
Coal dust 50g after taking devolatilization, is added in zirconia ball grinding jar, and 10ml dehydrated alcohol is added in ball grinder, is situated between
Matter ball selective oxidation zirconium ball, control medium ball gradation are middle ball: bead=1:1, ratio of grinding media to material=5:1, planetary ball mill revolving speed
300r/min, Ball-milling Time 10h obtain the microfine coal of favorable dispersibility, through laser particle size in vacuum oven after dry 4h
Tester measures the particle diameter distribution of coal dust, as shown in Fig. 2, D50=1.592 μm, D90=2.889 μm.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added to the mixing immersion liquid of hydrochloric acid and sodium fluoride
Middle removal of impurities, wherein concentration of hydrochloric acid is 3.6mol/L, and NaF concentration is 18g/L, and acidleach temperature is 60 DEG C, time 2h, and liquid-solid ratio is
15mL/g is filtered after acidleach, is washed to neutrality, and filter residue dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 99.67%.
Embodiment 3
It takes anthracite to be tentatively crushed to -200 mesh, is placed in corundum crucible, 650 DEG C of heat preservations in nitrogen atmosphere in Muffle furnace
4h, devolatilization.
Coal dust 50g after taking devolatilization, is added in zirconia ball grinding jar, and 10ml dehydrated alcohol is added in ball grinder, is situated between
Matter ball selective oxidation zirconium ball, control medium ball gradation are middle ball: bead=1:2, ratio of grinding media to material=10:1, planetary ball mill revolving speed
300r/min, Ball-milling Time 8h obtain the microfine coal of favorable dispersibility, through laser particle size in vacuum oven after dry 4h
Tester measures the particle diameter distribution of coal dust, as shown in figure 3, D50=1.536 μm, D90=2.937 μm.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added to the mixing immersion liquid of hydrochloric acid and sodium fluoride
Middle removal of impurities, wherein concentration of hydrochloric acid is 4.8mol/L, and NaF concentration is 15g/L, and acidleach temperature is 60 DEG C, time 2h, and liquid-solid ratio is
15mL/g is filtered after acidleach, is washed to neutrality, and filter residue dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 99.53%.
Comparative example 1
Take and be tentatively crushed to the raw coal 50g of -200 mesh, be added in zirconia ball grinding jar, be added in ball grinder 10ml without
Water-ethanol, medium ball selective oxidation zirconium ball, control medium ball gradation are middle ball: bead=1:1, ratio of grinding media to material=5:1, planetary ball
Mill speed 300r/min, Ball-milling Time 10h obtain the microfine coal of favorable dispersibility in vacuum oven after dry 4h, pass through
Laser particle analyzer measures the particle diameter distribution of coal dust, as shown in figure 4, D50=12.4 μm, D90=26.1 μm.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added to the mixing immersion liquid of hydrochloric acid and sodium fluoride
Middle removal of impurities, wherein concentration of hydrochloric acid is 3.6mol/L, and NaF concentration is 18g/L, and acidleach temperature is 60 DEG C, time 2h, and liquid-solid ratio is
15mL/g is filtered after acidleach, is washed to neutrality, and filter residue dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 99.27%.
Comparative example 2
It takes anthracite to be tentatively crushed to -200 mesh or so, is placed in corundum crucible, in Muffle furnace 650 DEG C in nitrogen atmosphere
Keep the temperature 4h, devolatilization.
Coal dust 50g after taking devolatilization, is added in zirconia ball grinding jar, and dehydrated alcohol, medium ball selective oxidation zirconium is not added
Ball, control medium ball gradation are middle ball: bead=1:1, ratio of grinding media to material=5:1, planetary ball mill revolving speed 300r/min, when ball milling
Between 10h obtain the microfine coal of favorable dispersibility in vacuum oven after dry 4h, measure coal dust through laser particle analyzer
Particle diameter distribution, as shown in figure 5, D50=17.5 μm, D90=40.1 μm.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added to the mixing immersion liquid of hydrochloric acid and sodium fluoride
Middle removal of impurities, wherein concentration of hydrochloric acid is 3.6mol/L, and NaF concentration is 18g/L, and acidleach temperature is 60 DEG C, time 2h, and liquid-solid ratio is
15mL/g is filtered after acidleach, is washed to neutrality, and filter residue dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 99.11%.
Comparative example 3
It takes anthracite to be tentatively crushed to -200 mesh, is placed in corundum crucible, 650 DEG C of heat preservations in nitrogen atmosphere in Muffle furnace
4h, devolatilization.
Coal dust 50g after taking devolatilization, is added in zirconia ball grinding jar, and 10ml dehydrated alcohol is added in ball grinder, is situated between
Matter ball selective oxidation zirconium ball, control medium ball gradation are middle ball: bead=1:1, ratio of grinding media to material=5:1, planetary ball mill revolving speed
300r/min, Ball-milling Time 10h obtain the microfine coal of favorable dispersibility in vacuum oven after dry 4h.
Microfine coal is uniformly mixed with the ethyl alcohol of 10wt% microfine coal, is added in hydrochloric acid and cleans, wherein hydrochloric acid is dense
Degree is 3.6mol/L, and acidleach temperature is 60 DEG C, time 2h, liquid-solid ratio 15mL/g, filters after acidleach, is washed to neutrality, is filtered
Slag dries to obtain the ultra-fine Filter Tuber For Clean Coal that purity is 98.97%.
Claims (10)
1. a kind of ball milling pretreatment-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, which is characterized in that include the following steps:
(1) coal particle is obtained after roasting in protective atmosphere after being crushed anthracite；Dispersion is added into resulting coal particle
Agent, control abrading-ball gradation are drying to obtain microfine coal after carrying out ball milling；
(2) it after mixing microfine coal with surfactant, is added in the mixing immersion liquid of acid and fluoride salt, after heated leaching
It is filtered, washed, is drying to obtain ultra-fine clean coal dust.
2. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), anthracite is crushed to -200 mesh.
3. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), the protective atmosphere is at least one of nitrogen, helium, argon gas；The maturing temperature is 400-800
DEG C, time 2-8h.
4. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), the dispersing agent is at least one of triethanolamine, alkyl enuatrol, polyethylene glycol, ethyl alcohol, addition
Amount is 1-100mL/300g coal particle.
5. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), the abrading-ball is at least one of stainless steel, hard alloy, polyurethane, zirconium oxide, agate, and gradation is
The quantity of big ball, middle ball and bead is 1:1-2 than the quantity ratio for 1:1-3:1-6 or middle ball and bead.
6. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), ball material mass ratio when ball milling is 5-20:1, rotational speed of ball-mill 200-500r/min, Ball-milling Time 6-
12h。
7. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (1), the drying mode is vacuum drying, and temperature is 70~90 DEG C or freeze-drying, and temperature is -10~-50
℃。
8. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (2), surfactant is selected from least one of ethyl alcohol, polyethylene glycol, triethanolamine and alkyl enuatrol, table
Face activating agent dosage is the 2-15wt% of microfine coal quality.
9. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (2), acid is selected from least one of nitric acid, hydrochloric acid；Acid concentration is 2.0-8.0mol/L；Fluoride salt is selected from fluorination
At least one of sodium, aluminum fluoride, lithium fluoride, calcirm-fluoride；Fluorination salinity is 5-30g/L.
10. ball milling pretreatment according to claim 1-chemical method combines the method for preparing ultra-fine Filter Tuber For Clean Coal, feature exists
In: in step (2), the liquid-solid ratio for mixing immersion liquid and microfine coal is 5-30mL/g；Heating extraction temperature is 40-90 DEG C；Heating
Extraction time is 1-5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110314767A (en) * | 2019-08-13 | 2019-10-11 | 中国矿业大学 | A kind of low order/oxidized coal slime floating agent and application method |
| CN110404634A (en) * | 2019-08-05 | 2019-11-05 | 中南大学 | A kind of method that multistage ball milling prepares microfine coal |
| CN115232658A (en) * | 2022-07-15 | 2022-10-25 | 广东一纳科技有限公司 | Ultra-pure anthracite and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039711A (en) * | 1988-07-22 | 1990-02-21 | 菲利普莫里斯生产公司 | Carbon heat source |
| CN102434343A (en) * | 2011-09-30 | 2012-05-02 | 辽宁科技大学 | Oxygen-enriched combustion method of lignite methyl alcohol coal slurry fuel material in compression-type internal combustion engine |
| WO2012142488A2 (en) * | 2011-04-15 | 2012-10-18 | Biogenic Reagents LLC | Methods and apparatus for enhancing the energy content of carbonaceous materials from pyrolysis |
| CN102786310A (en) * | 2012-07-18 | 2012-11-21 | 湖南汨特科技新材料股份有限公司 | Composite carbon block and its production technology |
| CN104176753A (en) * | 2014-06-03 | 2014-12-03 | 崔佩霞 | Method for extracting composite aluminum oxide from coal ashes |
| US20150166917A1 (en) * | 2011-09-07 | 2015-06-18 | Clean Coal Technologies, Inc. | Treatment of coal |
| CN106118133A (en) * | 2016-06-22 | 2016-11-16 | 上海汇友精密化学品有限公司 | A kind of preparation method of superfine disperse dye |
| CN108439396A (en) * | 2018-05-17 | 2018-08-24 | 哈尔滨工业大学 | The classifying porous charcoal preparation method of coal base coupled based on chemical activation and catalytic activation |
| CN108499724A (en) * | 2018-03-30 | 2018-09-07 | 中南大学 | A kind of deliming and desulphurizing method of sulphur coal |
| CN108659876A (en) * | 2018-05-18 | 2018-10-16 | 沈阳航空航天大学 | The method for preparing bio oil is combined in pretreatment of raw material with hydrothermal liquefaction |
-
2019
- 2019-05-09 CN CN201910384240.9A patent/CN110003965B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039711A (en) * | 1988-07-22 | 1990-02-21 | 菲利普莫里斯生产公司 | Carbon heat source |
| WO2012142488A2 (en) * | 2011-04-15 | 2012-10-18 | Biogenic Reagents LLC | Methods and apparatus for enhancing the energy content of carbonaceous materials from pyrolysis |
| US20150166917A1 (en) * | 2011-09-07 | 2015-06-18 | Clean Coal Technologies, Inc. | Treatment of coal |
| CN102434343A (en) * | 2011-09-30 | 2012-05-02 | 辽宁科技大学 | Oxygen-enriched combustion method of lignite methyl alcohol coal slurry fuel material in compression-type internal combustion engine |
| CN102786310A (en) * | 2012-07-18 | 2012-11-21 | 湖南汨特科技新材料股份有限公司 | Composite carbon block and its production technology |
| CN104176753A (en) * | 2014-06-03 | 2014-12-03 | 崔佩霞 | Method for extracting composite aluminum oxide from coal ashes |
| CN106118133A (en) * | 2016-06-22 | 2016-11-16 | 上海汇友精密化学品有限公司 | A kind of preparation method of superfine disperse dye |
| CN108499724A (en) * | 2018-03-30 | 2018-09-07 | 中南大学 | A kind of deliming and desulphurizing method of sulphur coal |
| CN108439396A (en) * | 2018-05-17 | 2018-08-24 | 哈尔滨工业大学 | The classifying porous charcoal preparation method of coal base coupled based on chemical activation and catalytic activation |
| CN108659876A (en) * | 2018-05-18 | 2018-10-16 | 沈阳航空航天大学 | The method for preparing bio oil is combined in pretreatment of raw material with hydrothermal liquefaction |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404634A (en) * | 2019-08-05 | 2019-11-05 | 中南大学 | A kind of method that multistage ball milling prepares microfine coal |
| CN110314767A (en) * | 2019-08-13 | 2019-10-11 | 中国矿业大学 | A kind of low order/oxidized coal slime floating agent and application method |
| CN115232658A (en) * | 2022-07-15 | 2022-10-25 | 广东一纳科技有限公司 | Ultra-pure anthracite and preparation method thereof |
| CN115232658B (en) * | 2022-07-15 | 2023-10-03 | 广东一纳科技有限公司 | Ultra-pure anthracite and preparation method thereof |
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|---|---|
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