CN111408481A - Coal slime plasma flotation deashing and desulfurization method - Google Patents
Coal slime plasma flotation deashing and desulfurization method Download PDFInfo
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- CN111408481A CN111408481A CN202010307061.8A CN202010307061A CN111408481A CN 111408481 A CN111408481 A CN 111408481A CN 202010307061 A CN202010307061 A CN 202010307061A CN 111408481 A CN111408481 A CN 111408481A
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- 238000005188 flotation Methods 0.000 title claims abstract description 132
- 239000003245 coal Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 65
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 65
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000009832 plasma treatment Methods 0.000 claims abstract description 31
- 238000004939 coking Methods 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 150000003463 sulfur Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008396 flotation agent Substances 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 9
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical group CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 7
- 230000002000 scavenging effect Effects 0.000 claims description 7
- 239000012991 xanthate Substances 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000003250 coal slurry Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000011707 mineral Substances 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 3
- 240000000233 Melia azedarach Species 0.000 description 3
- 235000019425 dextrin Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/08—Subsequent treatment of concentrated product
- B03D1/082—Subsequent treatment of concentrated product of the froth product, e.g. washing
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a coal slime plasma flotation deashing and desulfurization method, which comprises the following steps: (1) performing direct flotation deashing, namely adding water into sulfur-containing coking coal slime for size mixing to obtain first ore pulp, and then performing direct flotation deashing on the first ore pulp to obtain sulfur-containing flotation clean coal ore pulp and direct flotation tail coal; (2) performing plasma treatment, namely performing plasma treatment on the sulfur-containing flotation clean coal pulp obtained in the step (1) to obtain modified sulfur-containing flotation clean coal; (3) and (2) reverse flotation desulfurization, namely adding water into the modified sulfur-containing flotation clean coal obtained in the step (1) for size mixing to obtain second ore pulp, and then performing reverse flotation desulfurization on the second ore pulp to obtain a clean coal product with low ash and low sulfur. The method can effectively reduce the dosage of the reverse flotation reagent, ensure the quality of the flotation clean coal product and improve the reverse flotation selectivity.
Description
Technical Field
The invention belongs to the field of coal chemical industry, and particularly relates to a coal slime plasma flotation deashing and desulfurization method.
Background
Coking coal is an indispensable important raw material for the departments of metallurgy, casting, chemical industry and the like, but the coking coal resource reserves in China are limited, and only account for about 27 wt% of the coal resource reserves found in China, and about half of the coking coal is difficult to utilize due to high sulfur and high ash. In recent years, with the rapid development of the steel industry and the coking industry, the demand of coking coal is increasing, and more enterprises turn the attention to low-quality coking coal, so that the development of an efficient deashing and desulfurization method has great significance for improving the utilization rate of the coking coal and protecting the environment.
Flotation desulfurization usually adopts a reverse flotation method, the content of organic matter surface polar groups in combustible bodies is improved by adding an inhibitor, the floating of the organic matter is inhibited, and pyrite is enriched by adding collectors such as xanthate and the like, but the defects of poor selectivity and weak acting force exist.
Depressants for reverse flotation are generally organic compounds containing heteropolar groups, adsorbed primarily by association with hydrophobic groups on the organic surface. The quantity of polar groups on the surface of an organic matter is indirectly increased through the adsorption inhibitor, but on one hand, the adsorption acting force is weak and unstable, and on the other hand, the inhibition capacity is weakened by the electrostatic action among the polar groups and the steric hindrance effect of inhibitor molecules, so that the problem of how to improve the inhibition effect of reverse flotation is urgently needed to be solved.
Disclosure of Invention
The invention aims to provide a coal slime plasma flotation deashing and desulfurization method, which can effectively reduce the dosage of a reverse flotation reagent, ensure the quality of flotation clean coal and improve the selectivity of reverse flotation.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a coal slime plasma flotation deashing and desulfurization method comprises the following steps:
(1) direct flotation deashing
Adding water into sulfur-containing coking coal slime for size mixing to obtain first ore pulp, and then performing direct flotation deashing on the first ore pulp to obtain sulfur-containing flotation clean coal ore pulp and direct flotation tail coal;
(2) plasma treatment
Performing plasma treatment on the sulfur-containing flotation clean coal pulp obtained in the step (1) to obtain modified sulfur-containing flotation clean coal;
(3) reverse flotation desulfurization
And (2) adding water into the modified sulfur-containing flotation clean coal obtained in the step (1) for size mixing to obtain second ore pulp, and then carrying out reverse flotation desulphurization on the second ore pulp to obtain a low-ash low-sulfur clean coal product and reverse flotation tail coal.
As understood by persons skilled in the art, the sulfur-containing flotation clean coal obtained in the step (1) is positioned in the foam, and the foam obtained in the direct flotation is the sulfur-containing flotation clean coal pulp; the obtained tank bottom product is direct flotation tailing; and (4) the tank bottom product obtained in the step (3) is a clean coal product, and the obtained foam is reverse flotation tailing.
The method of the invention carries out plasma modification on the ore pulp of the sulfur-containing flotation clean coal obtained by subjecting the sulfur-containing coking coal slime to direct flotation deashing so as to excite, dissociate and ionize the surface molecules, thereby changing the group composition on the surface of the ore pulp and simultaneously still maintaining the body performance of the ore pulp to obtain the modified sulfur-containing flotation clean coal; therefore, the plasma modification can reduce the content of nonpolar groups on the surface of organic matters in the combustible body, the sulfur-containing flotation clean coal is subjected to plasma modification before reverse flotation, the inhibition capacity of the reverse flotation on the organic matters in the combustible body can be improved, the surface performance difference between the organic matters and sulfides in the combustible body is enlarged, the desulfurization is smooth, the use of an inhibitor in the reverse flotation can be avoided, the use amount of a reverse flotation reagent is effectively reduced, the quality (namely, the ash content and the sulfur content are small) of the clean coal obtained by the reverse flotation is ensured, and the selectivity of the reverse flotation is improved.
As understood by those skilled in the art, clean coal and coal slime are both mixtures of combustible bodies and inorganic minerals, and the plasma modification is mainly used for reducing the content of non-polar groups on the surface of organic matters in the combustible bodies in the coal slime.
Preferably, in the step (1), the particle size of the sulfur-containing coking coal slurry is less than or equal to 0.5mm, such as 0.5mm, 0.45mm, 0.4mm, 0.35mm, 0.3mm, 0.25mm, 0.2mm, 0.15mm, 0.125mm, 0.1mm, 0.074mm and 0.05 mm.
Preferably, in the step (1), the concentration of the first ore pulp is 60-120 g/L, such as 70 g/L, 80 g/L, 90 g/L, 100 g/L and 110 g/L.
It is understood by those skilled in the art that in step (1), the pH of the first pulp is 6-9, such as 7 and 8.
Preferably, in step (1), the positive flotation agent comprises a first collector and a frothing agent; wherein the first collecting agent is diesel oil, and the dosage of the first collecting agent is 1000-3000g/t, such as 1250g/t, 1500g/t, 1750g/t, 2000g/t, 2250g/t, 2500g/t and 2750 g/t; the foaming agent is 2# oil and/or n-butanol, and is used in an amount of 50-300g/t, such as 75g/t, 100g/t, 125g/t, 150g/t, 175g/t, 200g/t, 225g/t, 250g/t and 275 g/t.
In one embodiment, in the step (1), the positive flotation deashing process sequentially comprises roughing, scavenging and concentrating processes, for example, 1-2 times of roughing, 1 time of scavenging and 1 time of concentrating sequentially.
As known to those skilled in the art, roughing refers to the operation of performing preliminary separation on selected mineral raw materials during mineral separation; after rough concentration, the mineral raw materials are separated into two or more than two products of rough concentrate, middlings, tailings and the like; the roughed product is not qualified product, and the sorting is required to be carried out continuously. The concentration refers to the separation operation of further enriching the rough concentrate in order to improve the content of useful components of the rough concentrate and enable the rough concentrate to meet the industrial quality requirement in the beneficiation process. The scavenging refers to the sorting operation for further recovering useful components from the rough tailings during the mineral separation.
The concentration of the sulfur-containing flotation clean coal ore pulp obtained in the step (1) is 200-400 g/L, such as 250 g/L, 300 g/L and 350 g/L.
Preference is given toIn the step (2), the plasma is generated by dielectric barrier discharge at normal temperature and normal pressure, the gas source of the plasma is air, and the gas filling amount of the plasma is 10-30L/(min. m)2) For example, 12.5L/(min m)2)、15L/(min·m2)、17.5L/(min·m2)、20L/(min·m2)、22.5L/(min·m2)、25L/(min·m2) And 27.5L/(min m)2)
Those skilled in the art understand that plasma treatment is performed in a plasma reactor, such as a flat plate plasma reactor; the section of the plasma reactor is a cylinder, the diameter of the cylinder is far larger than the height of the cylinder, for example, the height-diameter ratio is not less than 10, the plasma reactor is made of quartz, and the top and the bottom of the plasma reactor are respectively made of insulating quartz; the plasma reactor is provided with a slurry inlet, an air inlet and a slurry outlet.
In the invention, the plasma treatment process is as follows: and (2) simultaneously introducing air and the sulfur-containing flotation clean coal ore pulp obtained in the step (1) into a plasma reactor through an air inlet and an ore pulp inlet respectively, placing the plasma reactor between an upper high-voltage electrode and a lower high-voltage electrode, keeping the liquid level of the sulfur-containing flotation clean coal ore pulp horizontally introduced into the plasma reactor below the air inlet, positioning the upper electrode above the sulfur-containing flotation clean coal ore pulp, generating air plasma by the introduced air under the high voltage of a dielectric barrier plasma reactor, modifying the sulfur-containing flotation clean coal ore pulp introduced into the plasma reactor, and discharging the modified sulfur-containing flotation clean coal ore pulp from an ore pulp outlet after the modification.
In the present invention, the gas charge amount of the plasma refers to the charge amount of air, and the unit of the gas charge amount is L/(min. m)2) In2"means the unit of the cross-sectional area of the plasma reactor, and the unit of the gas aeration amount" L/(min. m)2) "means passing 1m per minute2The gas quantity entering the plasma reactor from the cross section area of the plasma reactor, for example, the gas aeration quantity of the plasma is 10-30L/(min. m)2) "means passing 1m per minute2The cross-sectional area of the plasma reactor is 10-30L.
Preferably, in the step (2), during the plasma treatment, the sulfur-containing flotation clean coal obtained in the step (1) is fed into a plasma reactor and then subjected to the plasma treatment; wherein the upper electrode is positioned above the sulfur-containing flotation clean coal ore pulp in the plasma reactor, and the vertical distance between the upper electrode and the sulfur-containing flotation clean coal ore pulp in the plasma reactor is 0.5-1.5cm, such as 0.6cm, 0.7cm, 0.8cm, 0.9cm, 1.0cm, 1.1cm, 1.2cm, 1.3cm and 1.4 cm.
Preferably, in the step (2), the plasma treatment conditions are as follows: the processing voltage is 50-100V, such as 55V, 60V, 65V, 70V, 75V, 80V, 85V, 90V and 95V; the treatment current is 1.5-3A, such as 1.75A, 2A, 2.25A, 2.5A and 2.75A; the treatment time is 1-9min, such as 2min, 3min, 4min, 5min, 6min, 7min and 8 min.
Preferably, in the step (3), the concentration of the second ore pulp is 60-120 g/L, such as 70 g/L, 80 g/L, 90 g/L, 100 g/L and 110 g/L.
Preferably, in step (3), the reverse flotation reagent comprises a second collector; wherein the second collecting agent is xanthate and/or black powder, and the dosage of the second collecting agent is 200-500g/t, such as 250g/t, 300g/t, 350g/t, 400g/t and 450 g/t.
In the invention, the dosage of the positive flotation agent and the negative flotation agent is based on the dosage of the sulfur-containing coking coal slime in the step (1) which is the processing object of the invention, for example, the dosage of the first collecting agent is 3000g/t, which means that the dosage of the first collecting agent corresponding to the sulfur-containing coking coal slime in the step (1) is 3000g/t and 1000-.
In one embodiment, in the step (3), the reverse flotation deliming process sequentially comprises roughing, scavenging and concentrating processes, for example, 1-2 times of roughing, 1 time of scavenging and 1 time of concentrating sequentially.
Those skilled in the art understand that in the step (1) and the step (3), the rotation speed of the flotation machine is 1200-2000rpm, such as 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm and 1900 rpm; the aeration amount is 500-1000ml/min, such as 600ml/min, 700ml/min, 800ml/min and 900 ml/min.
The invention has the beneficial effects that:
according to the coal slime plasma flotation deashing and desulfurization method, plasma surface modification is carried out on the sulfur-containing flotation clean coal ore pulp obtained by subjecting the sulfur-containing coking coal slime to direct flotation deashing, so that the hydrophilicity of the coal slime is improved, the inhibiting capability of the reverse flotation on organic matters in combustible bodies can be improved without adding an inhibitor in the reverse flotation, the use of the inhibitor is avoided, the consumption of a reverse flotation reagent is effectively reduced, the quality of clean coal obtained by the reverse flotation (namely, the content of ash and sulfur is small) is ensured, and the selectivity of the reverse flotation is improved.
Detailed Description
The technical solution and the effects of the present invention will be further described by the following embodiments and examples. The following embodiments and examples are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The sources of the raw materials and the apparatus used in the examples and comparative examples are as follows:
diesel, cetane number 30, xu zhou lian zhong new energy science and technology limited;
2# oil, density 0.9 Kg/L, purity 60 wt%, light yellow liquid, xu zhou lian zhong new energy science and technology limited;
n-butanol: analytically pure, Shanghai Linfeng Chemicals Co., Ltd;
xanthate, containing 80 wt% of sodium xanthate and 0.2 wt% of free alkali, xu zhou lian zhong new energy science and technology limited;
black powder: the content of the alkyl dithiophosphate is more than 80 wt%, and the industrial grade Zibo Boshan Jili flotation agent factory;
dextrin, chemical pure, chemical reagents of the national drug group, ltd;
a flotation machine, an XFD-1.5L mining single-tank flotation machine, wherein the volume of a single tank is 1.5L, the maximum rotating speed is 2000rpm, and Nanchang Haifeng mining machine equipment Co., Ltd;
plasma processor, CTP-2000K, Sulman electronics, Inc., Nanjing.
Example 1(S1)
The coal slime plasma flotation deashing and desulfurization method comprises the following steps:
(1) direct flotation deashing
Adding water into sulfur-containing coking coal slime for size mixing to obtain first ore pulp, and then performing direct flotation deashing on the first ore pulp to obtain sulfur-containing flotation clean coal ore pulp and direct flotation tail coal; wherein,
in the sulfur-containing coking coal slime, the ash content is 23 wt%, the S content is 5.23 wt%, and the particle size is less than or equal to 0.25 mm;
the first pulp has a concentration of 60 g/L and a pH of about 7;
the positive flotation agent is a first collecting agent and a foaming agent; the first collecting agent is diesel oil, and the using amount of the first collecting agent is 3000 g/t; the foaming agent is 2# oil, and the dosage is 100 g/t;
the rotating speed of the flotation machine is 1800rpm, and the aeration quantity is 600 ml/min;
(2) plasma treatment
Performing plasma treatment on the sulfur-containing flotation clean coal pulp obtained in the step (1) to obtain modified sulfur-containing flotation clean coal; wherein,
the plasma is generated by dielectric barrier discharge at normal temperature and pressure, the gas source of the plasma is air, and the gas filling amount of the plasma is 15L/(min. m)2)；
When in plasma treatment, feeding the sulfur-containing flotation clean coal pulp obtained in the step (1) into a plasma reactor, and then carrying out plasma treatment; wherein the upper electrode is positioned above the sulfur-containing flotation clean coal ore pulp in the plasma reactor, and the vertical distance between the upper electrode and the sulfur-containing flotation clean coal ore pulp in the plasma reactor is 1 cm;
plasma treatment conditions were as follows: the treatment voltage is 50V, the treatment current is 2A, and the treatment time is 3 min;
(3) reverse flotation desulfurization
Adding water into the modified sulfur-containing flotation clean coal obtained in the step (2) for size mixing to obtain second ore pulp, and then carrying out reverse flotation desulfurization on the second ore pulp to obtain a clean coal product and reverse flotation tail coal; wherein,
the concentration of the second ore pulp is 100 g/L, and the pH is about 7;
the reverse flotation reagent is a second collector; the second collecting agent is xanthate, and the dosage is 400 g/t;
the rotating speed of the flotation machine is 1800rpm, and the aeration quantity is 600 ml/min.
Example 2(S2)
Example 2 differs from example 1 only in that:
the plasma treatment time was 1 min.
Example 3(S3)
Example 3 differs from example 1 only in that:
the plasma treatment time was 9 min.
Example 4(S4)
Example 4 differs from example 1 only in that:
the first pulp has a concentration of 120 g/L and a pH of about 7;
the positive flotation agent is a first collecting agent and a foaming agent; the first collecting agent is diesel oil, and the using amount of the first collecting agent is 2000 g/t; the foaming agent is No. 2 oil, and the dosage is 300 g/t;
the gas filling amount of the plasma is 10L/(min. m)2)；
During plasma treatment, the upper electrode is positioned above the sulfur-containing flotation clean coal ore pulp in the plasma reactor, and the vertical distance between the upper electrode and the sulfur-containing flotation clean coal ore pulp in the plasma reactor is 0.5 cm;
plasma treatment conditions were as follows: the treatment voltage is 100V, the treatment current is 1.5A, and the treatment time is 3 min;
the concentration of the second ore pulp is 120 g/L, and the pH is about 7;
the reverse flotation reagent is a second collector; the second collector is xanthate, and the dosage is 500 g/t.
Example 5(S5)
Example 5 differs from example 1 only in that:
the first pulp has a concentration of 90 g/L and a pH of about 7;
the positive flotation agent is a first collecting agent and a foaming agent; the first collecting agent is diesel oil, and the using amount of the first collecting agent is 1000 g/t; the foaming agent is n-butyl alcohol, and the dosage is 50 g/t;
the gas filling amount of the plasma is 30L/(min. m)2)；
During plasma treatment, the upper electrode is positioned above the sulfur-containing flotation clean coal ore pulp in the plasma reactor, and the vertical distance between the upper electrode and the sulfur-containing flotation clean coal ore pulp in the plasma reactor is 1.5 cm;
plasma treatment conditions were as follows: the treatment voltage is 70V, the treatment current is 3A, and the treatment time is 3 min;
the second pulp has a concentration of 60 g/L and a pH of about 7;
the reverse flotation reagent is a second collector; the second collecting agent is black powder, and the using amount is 200 g/t.
COMPARATIVE EXAMPLE 1(D1)
Comparative example 1 differs from example 1 only in that:
only the positive flotation deliming of step (1) is carried out, and step (2) and step (3) are not carried out.
COMPARATIVE EXAMPLE 2(D2)
Comparative example 2 differs from example 1 only in that:
step (2) is not carried out, and the sulfur-containing flotation clean coal obtained in step (1) is directly subjected to reverse flotation desulfurization in step (3); in the step (3), the reverse flotation reagent is a second collecting agent and an inhibitor; the second collecting agent is xanthate, and the dosage is 600 g/t; the inhibitor is dextrin, and the dosage is 2500 g/t.
The flotation results in examples 1-5 and comparative examples 1-2 are shown in tables 1 and 2, respectively.
Table 1 flotation results for examples 1-5
Note: j. the design is a square1 is justFlotation clean coal containing sulfur, W, from example 11 is justDirect flotation of tailings from example 1, J1 to-carrying outClean coal product of example 1, W1 toReverse flotation of the tailings from example 1; and the others are analogized in turn.
TABLE 2 flotation results of comparative examples 1-2
Note: j. the design is a square1 is just' -Sulfur-containing flotation clean coal of comparative example 1, W1 is just' -direct flotation of tailings from comparative example 1, J1 to' -clean coal product of comparative example 1, W1 to' -reverse flotation tailings from comparative example 1; and the others are analogized in turn.
According to the embodiments 1-5 and the table 1, the deashing and desulfurizing method disclosed by the invention can well remove ash and sulfur in the sulfur-containing coking coal slime, so that a low-ash low-sulfur clean coal product is obtained, and the price and the application range of the sulfur-containing coking coal slime are improved;
as can be seen from examples 1 to 3 and table 1, under the same conditions, the yield of the finally obtained clean coal product was improved, the ash content was increased, and the sulfur content was increased as the plasma treatment time was increased within a certain range; when the plasma treatment time is 1min, the yield of the finally obtained clean coal product is low, and although the sulfur content of the clean coal product is remarkably reduced, the loss of combustible bodies is more, mainly because the surface of the combustible bodies cannot be fully modified by the short-time plasma treatment, the combustible bodies still have certain floatability and are lost along with the floating of foams into the tail coal, and meanwhile, the ash content and the sulfur content in the clean coal product are low; when the plasma treatment time is increased to 3min, the combustible body is fully modified, so that the inhibiting effect of reverse flotation on organic matters in the combustible body is improved, the floatability of the combustible body is reduced, the loss of the combustible body is reduced, and the ash content and the sulfur content of a clean coal product are increased; when the plasma treatment time is increased to 9min, although the combustible body is fully modified, the floatability of the sulfur-containing minerals is easily reduced under the action of the plasma, so that part of the sulfur-containing minerals are difficult to float upwards and finally enter a clean coal product, and the ash content and the sulfur content in the clean coal product are relatively increased.
According to the comparison between the examples 1-5 and the comparative examples 1-2 and the tables 1-2, the method of the invention can improve the yield of the clean coal product and reduce the ash content and the sulfur content in the clean coal product, i.e. the yield and the quality of the clean coal product can be comprehensively improved and the value of the clean coal product can be improved;
according to the comparison between the example 1 and the comparative example 1, compared with the conventional direct flotation process (the comparative example 1), the method disclosed by the invention has the advantages that the sulfur content in the clean coal product can be obviously reduced by adopting the direct flotation and the reverse flotation after the plasma treatment, although a certain amount of combustible loss is brought by increasing the reverse flotation step, the sulfur content can be reduced to the qualified range (below 1 wt%), and the price and the application range of the clean coal product are greatly improved;
from the comparison between example 1 and comparative example 2, it can be seen that, although dextrin is used as an inhibitor, the sulfur content of the final clean coal product can be reduced to below 1 wt%, the yield of the clean coal product is also significantly reduced, indicating that the combustible loss is more, compared with the reverse flotation process (comparative example 2) using direct flotation and chemical agent as an inhibitor.
Claims (10)
1. A coal slime plasma flotation deashing and desulfurization method is characterized by comprising the following steps:
(1) direct flotation deashing
Adding water into sulfur-containing coking coal slime for size mixing to obtain first ore pulp, and then performing direct flotation deashing on the first ore pulp to obtain sulfur-containing flotation clean coal ore pulp and direct flotation tail coal;
(2) plasma treatment
Performing plasma treatment on the sulfur-containing flotation clean coal pulp obtained in the step (1) to obtain modified sulfur-containing flotation clean coal;
(3) reverse flotation desulfurization
And (3) adding water into the modified sulfur-containing flotation clean coal obtained in the step (2) for size mixing to obtain second ore pulp, and then carrying out reverse flotation desulphurization on the second ore pulp to obtain a clean coal product.
2. The method of claim 1,in the step (2), the plasma is generated by dielectric barrier discharge at normal temperature and normal pressure, the gas source of the plasma is air, and the gas inflation quantity of the plasma is 10-30L/(min. m)2)。
3. The method according to claim 1 or 2, characterized in that in the step (2), during plasma treatment, the sulfur-containing flotation clean coal ore pulp obtained in the step (1) is fed into a plasma reactor and then subjected to plasma treatment; wherein the upper electrode is positioned above the sulfur-containing flotation clean coal ore pulp in the plasma reactor, and the vertical distance between the upper electrode and the sulfur-containing flotation clean coal ore pulp in the plasma reactor is 0.5-1.5 cm.
4. The method according to any one of claims 1 to 3, wherein in the step (2), the plasma treatment conditions are as follows: the treatment voltage is 50-100V, the treatment current is 1.5-3A, and the treatment time is 1-9 min.
5. The method as claimed in any one of claims 1 to 4, wherein the sulfur-containing coking coal slurry in step (1) has a particle size of 0.5mm or less.
6. The process according to any one of claims 1-5, characterized in that in step (1), the first pulp has a consistency of 60-120 g/L.
7. The method of any one of claims 1 to 6, wherein in step (1), the positive flotation agent comprises a first collector and a frothing agent; wherein the first collecting agent is diesel oil, and the dosage of the first collecting agent is 1000-3000 g/t; the foaming agent is 2# oil and/or n-butanol, and the dosage of the foaming agent is 50-300 g/t.
8. The process according to any one of claims 1-7, characterized in that in step (3), the concentration of the second pulp is 60-120 g/L.
9. The method of any one of claims 1 to 8, wherein in step (3), the reverse flotation reagent comprises a second collector; wherein the second collecting agent is xanthate and/or black powder, and the dosage of the second collecting agent is 200-500 g/t.
10. The method according to any one of claims 1 to 9, wherein in the step (1), the positive flotation deashing process comprises a roughing process, a scavenging process and a concentration process in sequence; in the step (3), the reverse flotation desulfurization process sequentially comprises the processes of rough concentration, scavenging and fine concentration.
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