CN106281530B - A kind of method of alkali oxygen low-temperature oxidation Shengli Brown - Google Patents

A kind of method of alkali oxygen low-temperature oxidation Shengli Brown Download PDF

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CN106281530B
CN106281530B CN201610633780.2A CN201610633780A CN106281530B CN 106281530 B CN106281530 B CN 106281530B CN 201610633780 A CN201610633780 A CN 201610633780A CN 106281530 B CN106281530 B CN 106281530B
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alkali oxygen
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CN106281530A (en
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何润霞
刘全生
王斌
王丹丹
智科端
宋银敏
陈家明
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Inner Mongolia University of Technology
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
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Abstract

The invention discloses a kind of methods of alkali oxygen low-temperature oxidation Shengli Brown, are as made from following steps: by coal grinding, 105 DEG C of dry 4h obtain coal dust;Coal dust and NaOH solution are added in autoclave respectively, seal autoclave, leads to oxygen to 0.6MPa, by room temperature to 150-300 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample;Sample is filtered, filter residue is washed with distilled water, until pH=8, after in 105 DEG C of dry 4h, obtain different temperatures alkali oxygen low-temperature oxidation Shengli Brown.The invention enables Shengli Brown combustibilities, and significant change occurs, it is significantly reduced using this method treated its spontaneous combustion tendency of Shengli Brown, especially it is become apparent from 150-200 DEG C of alkali oxygen oxidation coal sample effect, the safety in coal saving and transportational process is substantially increased, there is significant economic and social benefit.

Description

A kind of method of alkali oxygen low-temperature oxidation Shengli Brown
Technical field
The invention belongs to technical field of coal chemical industry, and in particular to a kind of method of alkali oxygen low-temperature oxidation Shengli Brown.
Background technique
Main energy sources of the coal as China, high-efficiency cleaning are more important using the pollution that can not only mitigate to environment Be its become a kind of resource and important industrial chemicals.The Inner Mongol is one of the Large-scale Coal production province in China, and yield is only Inferior to Shanxi, coal reserves occupies national second.
Lignite is the maximum coal of reserves in the coal resources of the Inner Mongol, and wherein Shengli Coalfield is Xilinguole Beit area Maximum lignite coalfield, the reserves of lignite are 24,200,000,000 tons.Lignite spontaneous combustion can be adsorbed in air at normal temperature because of lignite Oxygen, and oxidation reaction occurs and generates heat, if the heat generated cannot distribute very well and continue to gather the temperature for making lignite Rise, the spontaneous combustion of lignite is just caused when reaching the ignition point of lignite.Lignite is lower compared with bituminous coal and anthracite ignition point, it is easier to Spontaneous combustion occurs.Especially Shengli Brown due to the high self-ignition index such as its high-moisture, high volatile and rich oxygen content cause its Production, storage, utilization, transport etc. are all extremely restricted, therefore its precondition being fully utilized is to make it can Long-time storage and long distance transportation, using being very restricted.Therefore, solve the problems, such as Shengli Brown spontaneous combustion for improving The utilization rate of lignite has very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of alkali oxygen low-temperature oxidation Shengli Brown, and using this method, treated Its spontaneous combustion tendency of Shengli Brown significantly reduces.
The present invention is achieved through the following technical solutions.
A kind of method of alkali oxygen low-temperature oxidation Shengli Brown, is as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave respectively, seal autoclave, lead to oxygen Gas is to 0.6MPa, by room temperature to 150-300 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, Obtain sample;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains different temperatures then in 105 DEG C of dry 4h Alkali oxygen low-temperature oxidation Shengli Brown.
The coal is the Shengli Brown in Xilinguole Beit area.
The coal dust and the mass ratio of NaOH solution are 1: 4-6.
The heating-up time is 1h.
The invention has the benefit that the method for alkali oxygen low-temperature oxidation Shengli Brown of the present invention, so that Shengli Brown burns Significant change occurs for performance, is significantly reduced using this method treated its spontaneous combustion tendency of Shengli Brown, especially with 150-200 DEG C Alkali oxygen oxidation coal sample effect becomes apparent from, and substantially increases the safety in coal saving and transportational process, has significant economical And social benefit.
Detailed description of the invention
Fig. 1 is the infrared spectrogram that product is made in embodiment 1-4 and comparative example 1-2;
Fig. 2 is the XRD spectrum and its Gauss matched curve figure that product is made in embodiment 1-4 and comparative example 1-2;
Fig. 3 is the Raman map and its Gauss matched curve figure that product is made in embodiment 1-4 and comparative example 1-2;
Fig. 4 is the CO that product burning is made in embodiment 1-4 and comparative example 1-22Production quantity and efficiency of carbon con version figure;
Fig. 5 is the TG/DTG combustion pattern of product made from embodiment 1-4 and comparative example 1-2.
In figure: SL-150 is embodiment 1;SL-200 is embodiment 2;SL-250 is embodiment 3;SL-300 is embodiment 4; SL-Raw is comparative example 1;SL-RT is comparative example 2.
Specific embodiment
Technical solution of the present invention is described in more detail with reference to the accompanying drawings and examples.
Embodiment 1
A kind of method of alkali oxygen low-temperature oxidation Shengli Brown, is as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave, seal autoclave, lead to oxygen extremely 0.6MPa, by room temperature to 150 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains 150 DEG C of alkali oxygen then in 105 DEG C of dry 4h Low-temperature oxidation Shengli Brown, is denoted as SL-150.
The coal is the Shengli Brown in Xilinguole Beit area.
The coal dust and the mass ratio of NaOH solution are 1: 4.
The heating-up time is 1h.
Embodiment 2
A kind of method of alkali oxygen low-temperature oxidation Shengli Brown, is as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave, seal autoclave, lead to oxygen extremely 0.6MPa, by room temperature to 200 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains 200 DEG C of alkali oxygen then in 105 DEG C of dry 4h Low-temperature oxidation Shengli Brown, is denoted as SL-200.
The coal is the Shengli Brown in Xilinguole Beit area.
The coal dust and the mass ratio of NaOH solution are 1: 5.
The heating-up time is 1h.
Embodiment 3
A kind of method of alkali oxygen low-temperature oxidation Shengli Brown, is as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave, seal autoclave, lead to oxygen extremely 0.6MPa, by room temperature to 250 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains 250 DEG C of alkali oxygen then in 105 DEG C of dry 4h Low-temperature oxidation Shengli Brown, is denoted as SL-250.
The coal is the Shengli Brown in Xilinguole Beit area.
The coal dust and the mass ratio of NaOH solution are 1: 5.
The heating-up time is 1h.
Embodiment 4
A kind of method of alkali oxygen low-temperature oxidation Shengli Brown, is as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave, seal autoclave, lead to oxygen extremely 0.6MPa, by room temperature to 300 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains 300 DEG C of alkali oxygen then in 105 DEG C of dry 4h Low-temperature oxidation Shengli Brown, is denoted as SL-300.
The coal is the Shengli Brown in Xilinguole Beit area.
The coal dust and the mass ratio of NaOH solution are 1: 6.
The heating-up time is 1h.
Comparative example 1
The Shengli Brown in Xilinguole Beit area is ground to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust, are denoted as SL-Raw。
Comparative example 2
A kind of method of room temperature alkali oxygen oxidation Shengli Brown, is as made from following steps:
1) Shengli Brown in Xilinguole Beit area is ground to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are uniformly mixed, are stirred under the revolving speed of air atmosphere 300r/min 3h stands 2h, obtains sample;
The coal dust and the mass ratio of NaOH solution are 1: 5;
3) sample is filtered, filter residue is washed with distilled water, and until pH=8, then in 105 DEG C of dry 4h, obtains room temperature alkali oxygen Shengli Brown is aoxidized, SL-RT is denoted as.
Industrial Analysis
Table 1 is the Industrial Analysis result that product is made in embodiment 1-4 and comparative example 1-2.
The Industrial Analysis result of product made from table 1 embodiment 1-4 and comparative example 1-2
As shown in Table 1, compared with comparative example 1, moisture, the content of ashes of embodiment 1-4 and comparative example 2 increase.Comparison The volatile matter content of example 2 slightly increases, and the volatile matter content of embodiment 1-4 reduces instead;And it is handled with alkali oxygen low-temperature oxidation The raising of temperature reduces amplitude and increases.
Fig. 1 is the infrared spectrogram that product is made in embodiment 1-4 and comparative example 1-2.As shown in Figure 1, room temperature alkali oxygen aoxidizes Functional group's variation of front and back coal sample (comparative example 1 and comparative example 2) is little, and different temperatures alkali oxygen low-temperature oxidation is to coal sample functional group Type and content have obvious influence.Wave number is in 3600-3000cm-1Between be hydroxyl absorption peak area, raw coal (comparative example 1) there are a wider absorption peaks in the section, and after the oxidation of room temperature alkali oxygen (comparative example 2), which has almost no change, and 150-200 DEG C of alkali oxygen low-temperature oxidation coal sample (embodiment 1 and embodiment 2) is more similar at the peak in the section, with 1 phase of comparative example Than, peak type narrows and intensity increases, when alkali oxygen low oxidation temperature is increased to 250-300 DEG C (embodiment 3 and embodiment 4), Absorption peak strength of the coal sample in this section is bigger.Above-mentioned phenomenon shows that the oxidation of room temperature alkali oxygen influences less hydroxyl in lignite, but After alkali oxygen low oxidation temperature increases, the hydroxy radical content of coal sample is obviously increased.Wave number is in 3000-2800cm-1Between be aliphatic The absorption vibrating area of C-H, 2923cm-1、2857cm-1Correspond respectively to-CH in cycloalkane or aliphatic hydrocarbon3With-CH2Asymmetry and Symmetrical stretching vibration.Comparative example 1 is relatively sharp in this absorption peak at two, after different temperatures alkali oxygen oxidation processes, 2925cm-1、 2848cm-1The absorption peak at place weakens, and out of -200 DEG C of room temperature, with the raising of alkali oxygen oxidation temperature, almost disappears, When treatment temperature is increased to 250-300 DEG C, the absorption peak at this occurs again, illustrates that the processing of alkali oxygen low-temperature oxidation makes the rouge in coal Fat hydrocarbon side chain is reduced, and 150-200 DEG C is reduced at most.Wave number is in 1700cm-1Neighbouring peak is that the stretching vibration of carbonyl (C=O) is inhaled Receive peak, it is considered that absorption peak is as caused by-COOH at this in coal, and comparative example 1 and 2 coal sample of comparative example can be seen at this Faint absorption peak, and exist in the form of acromion, and be then hardly visible at this in different temperatures alkali oxygen low-temperature oxidation coal sample Absorption peak illustrates in comparative example 1 and comparative example 2 with the presence of a small amount of carboxyl, and after higher temperature alkali oxygen low-temperature oxidation, Carboxyl is sharply reduced in coal, therefore the absorption peak at this disappears.Wave number 1600cm-1And 1580cm-1The peak at place is phenyl ring skeleton C=C stretching vibration absworption peak, this absorption peak at two does not change much after different temperatures alkali oxygen low-temperature oxidation, illustrates lignite Main body framework structure be not destroyed.1100cm-1、1030cm-1Absorption peak belong to the flexible of Si-O-Si in minerals Vibration, after the oxidation of room temperature alkali oxygen, which has no significant change, but the two peaks in 150-200 DEG C of alkali oxygen low-temperature oxidation coal sample Weaken, and the two peaks occur again in 250-300 DEG C of alkali oxygen low-temperature oxidation coal sample, illustrate the oxidation of room temperature alkali oxygen to minerals In SiO2It influences less, and in 150-200 DEG C of alkali oxygen low temperature oxidization process, part SiO2Generation is reacted with NaOH Na2SiO3, so 1100cm-1And 1030cm-1The peak at place weakens, and when alkali oxygen low-temperature oxidation is warming up to 250-300 DEG C, sodium metasilicate Na occurs2SiO3+2H2O==H2SiO3+ 2NaOH hydrolysis, and the H generated2SiO3It is heated to be decomposed into SiO again2(JCPDS 82-1574) and H2O, so SiO occur in 2 θ=24.23 ° in 250-300 DEG C of alkali oxygen low-temperature oxidation coal sample again2(JCPDS Absorption peak 82-1574).
Fig. 2 is the X ray diffracting spectrum and its Gauss matched curve figure that product is made in embodiment 1-4 and comparative example 1-2. By Fig. 2 (a) as it can be seen that each product is within the scope of 10-35 ° a wider diffraction maximum, which folded by γ and 002 two peak Add, wherein the peak γ is between 10-20 °, and 002 peak is between 20-35 °.002 peak is usually by crystallite fragrant in coal sample Structure is accumulated.Above-mentioned coal sample is carried out swarming fitting (using one of sample as representing, such as Fig. 2 (b)), and according to The microcrystalline silicon solar cells of Blagg and Scherrer equation calculation coal sample, the i.e. interlamellar spacing (d of aromatic structure002), fragrant synusia heap Product height (Lc) and fragrant synusia diameter (La), further according to formulaCalculate the coalification journey of coal sample Degree, that is, be condensed the percentage of aromatic layer ring, and microcrystalline silicon solar cells calculated result is shown in Table 2.
The microcrystalline silicon solar cells of product are made in table 2 embodiment 1-4 and comparative example 1-2
Note: d002: aromatic structure interlamellar spacing;Lc: fragrant synusia piling height;La: the size of fragrant synusia;P: coalification journey Degree
002 peak of natural graphite is located at 26.6 °, and as can be seen from Table 2,002 peak of six kinds of coal samples is respectively less than 26.6 °, Except raw coal 002 peak, 2 θ=22.74 ° from 26.6 ° compared with far ultraviolet, the angle of diffraction of remaining coal sample illustrates these between 24-25 ° Coal sample all has the structure of class graphite.The degree of graphitization of raw coal is lower, and after the oxidation of alkali oxygen, the degree of graphitization of coal sample is bright It is aobvious to increase, and with the raising of alkali oxygen low oxidation temperature, the angular higher angle offset of diffraction, when alkali oxygen low oxidation temperature The angle of diffraction reduces when increasing to 250-300 DEG C, but is higher than raw coal and room temperature alkali oxygen oxidation coal sample.The aromatic structure interlamellar spacing of raw coal d002=0.3745nm, the interlamellar spacing of coal sample is respectively less than raw coal, but its fragrant synusia piling height after the processing of alkali oxygen low-temperature oxidation Lc, fragrant synusia size La and degree of coalification P increase, cause coal aromatisation structure to have after illustrating the processing of alkali oxygen low-temperature oxidation Sequence enhancing, when alkali oxygen low-temperature oxidation treatment temperature is 150-200 DEG C, degree of coalification is maximum.
Fig. 3 is Raman spectrum and the Gauss matched curve (matched curve that product is made in embodiment 1-4 and comparative example 1-2 Using one of figure as representative).Two apparent raman frequency vibration areas are respectively belonging to the peak D (1340- in figure 1380cm-1) and the peak G (1580-1600cm-1), the peak D and the peak G respectively represent the defects of coal peak and (are commonly referred to be in plane Caused by defect and heteroatomic vibration) and coal in biggish aromatic ring structure.As seen from the figure, the intensity at the peak D and the peak G is with alkali oxygen The raising of oxidation temperature and increase, 150-200 DEG C reaches maximum, and 250-300 DEG C is weakened instead.Raman spectrum parameter is intended It closes result and is listed in table 3.I thereinD/IGIt has been widely used in studying crystal and graphite-like structure, generation as an important parameter The surface defect degree (disordered carbon of marginal portion) of table coal, the ratio is smaller, then the degree of graphitization of sample is higher, defect journey It spends smaller.Seen from table 3, after the processing of different temperatures alkali oxygen low-temperature oxidation, ID/IGIt reduces, is especially 150-200 with treatment temperature DEG C when, reduce at most, illustrate the coal sample defect bit quantity handled in this temperature range reduction, under lattice defect structure proportion Drop.When treatment temperature increases to 250-300 DEG C, the defect level of coal sample increases instead, consistent with XRD characterization result.The peak S master That to be indicated is-Sp in coal3- the CH of hydridization3Group and Car-Cal aromatic ring side chain, Is/IGIt is bigger, contained aromatic proton rouge in coal sample The ratio of fat side chain is higher, and aromatic proton aliphatic side chains are reduced in coal after the processing of alkali oxygen low-temperature oxidation, 150-200 DEG C of alkali oxygen cryogenic oxygen It is minimum to change aromatic proton aliphatic side chains in coal sample.IGL/IGBigger, the content of carbonyl is higher, as seen from the table, at alkali oxygen low-temperature oxidation After reason, the content of carbonyl declines, and illustrates that-COOH the partial exfoliation being connected in coal with phenyl ring or fat enters in solution.GRPeak, VLPeak and VRMain representative 3-5 phenyl ring in peak forms the sp of polymerization aromatic ring and be connected with aromatic ring methyl and methylene2-sp3Structure, ID/I(DR+VR+VL)It is bigger, show that the methyl being connected directly with phenyl ring, methylene content are lower, the variation of data illustrates alkali from table The processing of oxygen low-temperature oxidation leads to the sp being connected with aromatic ring2-sp3Valence bond structure is changed.
The Raman fitting parameter of product is made in table 3 embodiment 1-4 and comparative example 1-2
Fig. 4 is the CO that product burning is made in embodiment 1-4 and comparative example 1-22Production quantity and efficiency of carbon con version figure.It can be with by figure Know when the coal sample of comparative example 1 is burnt in air atmosphere, only there is larger amount of CO at 340 DEG C or so2It generates.Room temperature alkali oxygen oxygen Change coal sample and two CO then occurs2Peak is generated, is located at 200 DEG C and 640 DEG C, and the intensity at the latter peak is much larger than first Peak illustrates CO2Mainly generated at 640 DEG C or so, when alkali oxygen low oxidation temperature is increased to 150-200 DEG C, CO2Peak temperature out 760-770 DEG C is put off until, 320-330 DEG C is improved compared with comparative example 1, compared with comparative example 2CO2It mainly generates temperature and improves 120- 130 DEG C, and only one peak.When alkali oxygen low oxidation temperature is increased to 250-300 DEG C, CO2Peak temperature reduces instead out, and There are three CO2Generate peak.Above the experiment results show that alkali oxygen low-temperature oxidation makes lignite burning generate CO2Temperature improve , in room temperature within the scope of 200 DEG C, with the raising of alkali oxygen low oxidation temperature, generate CO2Temperature improve, but when temperature After degree reaches 250 DEG C, CO is generated2Temperature reduce instead, by a CO2It generates peak and becomes three CO2Generate peak.
Fig. 5 is the TG/DTG combustion pattern that product is made in embodiment 1-4 and comparative example 1-2.It can from TG curve Out, for each coal sample main weightless (initiation temperature) after 300 DEG C, the weight loss rate of 1 coal dust of comparative example is very fast, and passes through alkali oxygen oxygen The equal weakened at different degrees of weight loss rate before 500 DEG C of coal sample after change, room temperature alkali oxygen aoxidize coal sample weight loss rate and are less than comparison 1 coal sample of example is greater than other temperature alkali oxygen low-temperature oxidations and handles coal sample, and 150-200 DEG C of alkali oxygen low-temperature oxidation processing coal sample is in 760- Weight loss rate before 790 DEG C is most slow, and burning weight loss main peak is mobile to high-temperature region, and there are apparent combustion lag phenomenons, say Bright 150-200 DEG C of alkali oxygen low-temperature oxidation processing is substantially reduced the chemical oxidation performance of coal sample, and ignition temperature greatly improves, spontaneous combustion Tendency reduces.
In order to intuitively illustrate the spontaneous combustion tendency of each coal sample, the ignition temperature of coal sample need to be determined, calculated using TG-DTG method The ignition temperature for obtaining raw coal is 310.40 DEG C, is increased to 405.96 DEG C after room temperature alkali oxygen oxidation processes, 150-200 DEG C of alkali oxygen is low After warm oxidation processes, ignition temperature is increased substantially, and increases to 740-760 DEG C by 310.40 DEG C of raw coal, continues to improve alkali oxygen To 250-300 DEG C, ignition temperature (410-440 DEG C) declines low-temperature oxidation treatment temperature instead, is higher than 1 coal sample of comparative example and room temperature Alkali oxygen aoxidizes coal sample, but much smaller than 150-200 DEG C alkali oxygen low-temperature oxidation handles coal sample.
The foregoing is only a preferred embodiment of the present invention, the scope of protection of the present invention is not limited to this, it is any ripe Know those skilled in the art within the technical scope of the present disclosure, the letter for the technical solution that can be become apparent to Altered or equivalence replacement are fallen within the protection scope of the present invention.

Claims (4)

1. a kind of method of alkali oxygen low-temperature oxidation Shengli Brown, which is characterized in that be as made from following steps:
1) by coal grinding to 80-100 mesh, 105 DEG C of dry 4h obtain coal dust;
2) NaOH solution of coal dust and 0.5mol/L are added in autoclave respectively, seal autoclave, lead to oxygen extremely 0.6MPa, by room temperature to 150-300 DEG C under the revolving speed of 300r/min, constant temperature 1h when final temperature, after be cooled to room temperature, obtain sample Product;
3) sample is filtered, filter residue is washed with distilled water, until pH=8 obtains different temperatures alkali oxygen then in 105 DEG C of dry 4h Low-temperature oxidation Shengli Brown.
2. the method according to claim 1, wherein the coal is brown for the triumph in Xilinguole Beit area Coal.
3. the method according to claim 1, wherein the coal dust and the mass ratio of NaOH solution are 1: 4-6.
4. the method according to claim 1, wherein the heating-up time is 1h.
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