CN102249229A - Process using flotation process for preparing activated carbon with high specific surface area by fly ash - Google Patents
Process using flotation process for preparing activated carbon with high specific surface area by fly ash Download PDFInfo
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- CN102249229A CN102249229A CN 201110158847 CN201110158847A CN102249229A CN 102249229 A CN102249229 A CN 102249229A CN 201110158847 CN201110158847 CN 201110158847 CN 201110158847 A CN201110158847 A CN 201110158847A CN 102249229 A CN102249229 A CN 102249229A
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- flotation
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- fly ash
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- 238000005188 flotation Methods 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 230000008569 process Effects 0.000 title claims abstract description 83
- 239000010881 fly ash Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000008396 flotation agent Substances 0.000 claims abstract description 16
- 230000033001 locomotion Effects 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 66
- 239000002956 ash Substances 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 41
- 230000004913 activation Effects 0.000 claims description 30
- 239000003546 flue gas Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 239000000567 combustion gas Substances 0.000 claims description 15
- 239000013618 particulate matter Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 230000007420 reactivation Effects 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001994 activation Methods 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 description 17
- 239000010883 coal ash Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000007667 floating Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229960000411 camphor oil Drugs 0.000 description 2
- 239000010624 camphor oil Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000754779 Brycinus imberi Species 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
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Abstract
The invention discloses a process using a flotation process for preparing activated carbon with high specific surface area by fly ash. The process comprises the flotation process of fly ash particles and the activation process of the floated carbon-containing particles. The flotation process comprises the following steps: (1) adding a flotation agent to the fly ash particles to form a mixed material; (2) allowing the mixed material obtained in step (1) to fall from the upper part in flotation equipment; (3) forming gas moving upwards in the flotation equipment, wherein, the gas and the mixed material falling in step (2) form countercurrent contact and the gas is in a turbulent condition during the upward movement process; and (4) collecting the particles which pass through a flotation plate of the flotation equipment upwards in step (3). During the flotation process, the gas which blows upwards bubbles and the particles is in the turbulent condition, thus reaching better flotation effect and higher flotation rate. By utilizing the process, the activated carbon can be prepared from the fly ash, and the obtained activated carbon has high added value and high specific surface area.
Description
Technical field
The present invention relates to utilize flyash to make gac, more particularly, the present invention relates to a kind of technology that adopts flotation process by the flyash preparing active carbon.
Background technology
Flyash is one of bigger industrial residue of the current discharge capacity of China, present stage China's year bed drain purge reached 3,000 ten thousand tons.Along with development of electric power industry, the flyash quantity discharged of coal-burning power plant increases year by year.Contain a large amount of unburned carbon granules in the flyash, after flotation, can be used as the raw material of making gac.
Chinese patent 200810143173.3 discloses a kind of novel process of producing gac with flyash, raw material be boiler of power plant dump the former ash of material flyash, after box tube blower is handled, join in the ore pulp pretreater, dispersion agent and composite floating chemical also join in the ore pulp pretreater through automatic medicament feeding machine simultaneously, and then enter first step flotation column, in the flotation column of the second stage, the carbon particles of separating from second stage flotation column, carbon content reaches more than 85%, meet the carbon content requirement of gac, through thickner, filter, behind the dryer, enter the special-purpose mill of gac, feed high pressure steam, further levigate, after oily water separation and oven dry become gac.
Chinese patent 99115444.4 discloses a kind of flyash and floating tail-coal method for floating and technology again, tail coal and coal ash are sent into draining screen implementation sorting, + coal and foreign material more than the 0.5mm granularity are directly screened, following tail coal of general-0.5mm granularity or coal ash and water are with make up water and mix according to the characteristic of tail coal and the coal ash special flotation reagent with x axle, Korean pine oil and hydrocarbon-type oil formulated in combination again, coal flotation again in flotation machine, thus the combustiblematerials in tail coal or the coal ash is all flotated.
Chinese patent 200410098980.X discloses the flotation column process of carbon residue in a kind of separation of fine coal ash, is made of ore pulp preparation, flotation column sorting, product three parts of dewatering.Adopt the dual-jet flotation column, and cooperate corresponding feed and dehydration equipment, form flotation column-chamber-type press filter floatation process, remove the uncombusted carbon granule in the flyash.With high concrete carbon fly ash and the water agitation vat of packing into, be prepared into the ore pulp that meets the floatation concentration requirement through the impeller stirring, the ore pulp for preparing is delivered to the feeding mouth of flotation column with spiral pump, the ore pulp pan feeding obtains flotation concentrate slurry carbon residue and flotation tailing pulp flyash through the sorting of dual-jet flotation column, processing by the chamber-type press filter dehydration obtains final carbon residue product and flyash product respectively.
Chinese patent 200810031473.2 discloses a kind of technique for decarbonizing fly ash with high ignition loss, the former ash of flyash is transported to the bulk cement storage tank of treatment plant by tank car in bulk, send into after metering in the ore pulp pretreater, automatic medicament feeding machine also adds dispersion agent, composite floating chemical in the ore pulp pretreater, mix stirring, output after the ore pulp pretreater is handled enters the coal ash flotation pillar special, through flotation, carbon granule and tail ash content from, carbon granule of collecting respectively and tail ash are concentrated through thickner respectively again, become fine coal powder and low loss on ignition flyash behind the filter filter dehydration.
Chinese patent 200810031474.7 discloses a kind of flotation pillar special for fly ash, at flotation column cylindrical shell top pulp distributor is housed, establish multilayer bubbling plate in the cylindrical shell, multiple spot swirl-flow devices and multiple spot tail ash overflow weir are established in the cylindrical shell bottom, install the ore pulp distribution piping around the pulp distributor, cylindrical shell peripheral device circulating line, the circulating line upper end connects with the ore pulp distribution piping, lower end and swirl-flow devices connect, ore pulp distribution piping interface is connected the recycle pump two ends respectively with feed inlet and outlet, high-carbon balanced overflow plate of ash and high-carbon ash overflow collection mouth also are housed on flotation column top, and tail ash overflow weir is equipped with tail ash automatic control stuff box by pipe connection.
The shortcoming of technique scheme is, feeding the gas that drives bubble and particle motion in the floatation equipment is laminar flow or eddy flow, and flotation effect is poor, and the flotation rate is low.
Summary of the invention
At the shortcoming of prior art, the purpose of this invention is to provide a kind of technology of utilizing flyash to make active carbon with high specific surface area, in floatation process, it is with bubble and particle motion in the gas-powered floatation equipment of turbulent state.
To achieve these goals, the invention provides a kind of technology that adopts flotation process by the flyash preparing active carbon, it comprises flyash is carried out the process of flotation and the particulate state carbonaceous material that floatingly selects is carried out the activatory process;
Wherein, floatation process comprises the steps:
1. in fly ash grain, add flotation agent, form mixture;
2. in floatation equipment, make step 1. in the mixture of gained fall from top;
3. in floatation equipment, form the gas upwards blow, the mixture formation counter current contact that this gas and step fall in 2., and also this gas is turbulent state in the process that moves upward;
4. collect step 3. in the particulate matter of the flotation plate by floatation equipment upwards.
1. middle flotation agent, the collecting agent of using of step, wherein, the flotation agent of employing is pine camphor oil or C8 aronmatic, collecting agent is LIGHT DIESEL OIL or diesel oil.3. the gas in is specially 1-2 normal atmosphere (gauge pressure).
The principle of work of this floatation process is: the main component of flyash is carbon granule and ash content.After adding flotation agent and/or collecting agent and/or other auxiliary agent, the particle in the flyash contacts, collides with bubble, and the carbon granule that flotability is good optionally adheres to bubble, and is carried rising, realizes flotation.The ash content of flotability difference is then to sinking.
Because upwards blow bubble and particulate gas is turbulent state, thereby the better effects if of flotation, the flotation rate is higher.
Reactivation process comprises the steps:
A with potassium hydroxide, carbon dust according to 6-2: 1 weight ratio mixes, and puts into activation furnace;
B feeds nitrogen in activation furnace, discharge air wherein, adopts the method for temperature-gradient method-insulation simultaneously, is warming up to 700 ℃-1000 ℃, preferably is warming up to 700 ℃-900 ℃;
C imports the gas that activation furnace produced and fills in the encloses container of water, carry out water seal and reclaim, and this encloses container further is provided with the pneumatic outlet after water seal is reclaimed;
D lowers the temperature activation furnace, and products therefrom washs, drying, obtains the gac of high-specific surface area.
Potassium hydroxide is activator, and the reaction at high temperature of itself and carbon dust is:
KOH+C→K
2CO
3+K
2O+H
2
KOH, K
2CO
3, K
2O forms etching to single graphite microcrystal or crystallite group and generates the hole in different apertures, and the micro-molecular gas that reaction generates in the reactivation process is as CO, CO
2, H
2, H
2O, H
2S etc., in the effusive process in existing duct, Yin Gaowen expands and plays the effect of reaming.In addition, the potassium metal steam that produces in the activatory process will enter graphite layers, the effect of performance pore-creating, reaming.
Most of potassium steam all reacts in the priming reaction process, thereby only remaining a spot of unreacted potassium steam, by step c the gas that activation furnace produced is imported to fill in the encloses container of water, carries out water seal and reclaims, and makes K
2CO
3Steam, K
2O steam and a spot of potassium steam are all absorbed by water, utilize simple method and lower cost to realize the recovery of reaction back gas.
According to an embodiment of the present invention, in floatation process, turbulent state is by the different multiply upward air stream of gas angulation in floatation equipment is formed.For example, diffusing device of air can be set in floatation equipment, the surface of this diffusing device of air is provided with a plurality of pores, and these a plurality of pores are set to point to oblique upper with different angles separately, so that the material in the floatation equipment forms turbulent flow.
According to another embodiment of the present invention, in floatation process, the container at the mixture place during upwards 1. the particulate matter by the flotation plate then is transported to so that upwards the particulate matter by the flotation plate enter floatation equipment once more and carry out flotation, and then improve utilization ratio of raw materials.
According to another embodiment of the present invention, in floatation process, use ultrasonic separation means or ultrasonic broken in bulk putting in the floatation equipment, improve peeling off of carbon granule and ash content by the emission ultrasonic wave, form granularity and reach 10,000 purpose superfine carbon granules.Particularly, this ultrasonic separation means or ultrasonic broken in bulk putting comprise ultrasonic transmitter and supporting supplementary unit.
According to another embodiment of the present invention, in floatation process, plane of reflection is set in the floatation equipment, make mixture that falls from the top and the particle that is passed down through the flotation plate that reflection upwards take place.This plane of reflection can be, for example the different shapes such as awl bucket of plane, sphere, point upward.
According to another embodiment of the present invention, in floatation process, feed downward gas at mixture, so that the speed that mixture falls smoothly and control is fallen, this gas is specially 1-2 normal atmosphere (gauge pressure).
Said process is first step flotation.In addition, in order to obtain the carbon granule that granularity is littler, precision is higher, can carry out second stage flotation to the carbon granule that floatingly selects, its concrete steps are as follows:
5. in floatation equipment, make step 4. in the particulate matter of gained fall from top;
6. in floatation equipment, form the gas upwards blow, the particulate matter formation counter current contact that this gas and step fall in 5., and also this gas is turbulent state in the process that moves upward;
7. collect step 6. in the particulate matter of the flotation plate by described floatation equipment upwards.
Step 1., 2., 3., 4. in used floatation equipment be first floatation equipment, step 5., 6., 7. in used floatation equipment be second floatation equipment.6. the gas in is specially 1-2 normal atmosphere (gauge pressure).
According to another embodiment of the present invention, in floatation process, step 4., also comprise the steps: between 5. to step 4. in the particulate matter of gained add flotation agent and collecting agent; Wherein, the flotation agent of employing is pine camphor oil or C8 aronmatic, and collecting agent is LIGHT DIESEL OIL or diesel oil.
According to another embodiment of the present invention, in floatation process, plane of reflection is set in the floatation equipment, reflection upwards takes place in particle that falls from the top in making 5. and the particle that is passed down through the flotation plate.This plane of reflection can be, for example the different shapes such as awl bucket of plane, sphere, point upward.
According to another embodiment of the present invention, the step of floatation process 5. in, in particle, feed downward gas so that the speed that it falls smoothly and control is fallen, this gas is specially 1-2 normal atmosphere (gauge pressure).
According to another embodiment of the present invention, in reactivation process, carbon dust comprises the particulate state carbonaceous material that obtained by the fly ash grain flotation (it specifically can be the powdered carbon or the powdered carbon of charing not after the charing) and refinery coke, and its weight ratio is 2: 8-8: 2, be preferably 3: 7-7: 3.
According to another embodiment of the present invention, in reactivation process, back effluent air from encloses container is reclaimed in water seal filter, to remove solid particulate wherein, emptying then.
According to another embodiment of the present invention, in reactivation process, temperature-gradient method-insulation divides three sections and carries out; Wherein, in first section, be warming up to 380 ℃-440 ℃, then insulation; In second section, be warming up to 480 ℃-560 ℃, then insulation; In the 3rd section, be warming up to 700 ℃-900 ℃, then insulation.
According to another embodiment of the present invention, in reactivation process, the speed that feeds nitrogen among the step b is so control, be warming up to 100 ℃-300 ℃, preferred 100 ℃-200 ℃, more preferably 100 ℃-160 ℃ the time, the air in the activation furnace is discharged substantially.
According to another embodiment of the present invention, in reactivation process, in the steps d described activation furnace is cooled to 100 ℃-200 ℃, preferred 100 ℃-160 ℃.
According to another embodiment of the present invention, in reactivation process, refinery coke is crushed to the 60-100 order.
According to another embodiment of the present invention, the particulate state carbonaceous material that the fly ash grain flotation obtains can carry out charing earlier, then the powdered carbon after the charing is activated, and this carbonization process comprises the steps:
A utilizes heating unit, and the powdered carbon raw material in the rotating cylinder of charring furnace is heated, and this powdered carbon raw material produces combustible combustion gas under heat effect;
B closes heating unit;
C feeds the combustion gas that steps A produced in the combustion unit and burns, and produces high-temperature flue gas;
D feeds rotating cylinder with the high-temperature flue gas that is produced, and the powdered carbon raw material is heated, and produces combustible combustion gas;
The combustion gas that E is produced step D feeds in the described combustion unit burns, and produces high-temperature flue gas;
F repeated execution of steps D and step e.
" powdered carbon raw material " alleged among the present invention refers in particular to the raw material of charing in charring furnace, its particulate state carbonaceous material for being made by the fly ash grain flotation.
" combustion gas " alleged among the present invention refers in particular to the inflammable gas that the powdered carbon raw material produces under heat effect, it can comprise CO, H
2, CH
4, alkane, alkene, the various volatile components of coal tar wet goods; Alleged " flue gas " is the gas that is produced after combustion gas is burnt in combustion unit.Method of the present invention promptly by these inflammable gass of burning, provides the charing of powdered carbon raw material needed heat.The inflammable gas that produces in the carbonization process feeds in the combustion unit and burns, and the high-temperature flue gas that burning produces feeds charring furnace, and the powdered carbon raw material in the charring furnace is heated and then charing.Like this, both save the energy, and avoided a large amount of inflammable gass to enter in the atmosphere again, reduced environmental pollution.
According to another embodiment of the present invention, in carbonization process,, rotating cylinder is rotated, thereby the powdered carbon raw material is rolled, thereby make powdered carbon raw material thermally equivalent in the heated while of powdered carbon raw material.
According to another embodiment of the present invention, in carbonization process, be provided with the device that drives the motion of powdered carbon raw material in the rotating cylinder, as raise plate, blade, thrust etc.The purpose of She Zhiing is in the process of heating like this, pushes the powdered carbon raw material and moves ahead in rotating cylinder, to realize continuity production.In order to reach better propelling movement effect, these are a plurality of raise plate, blade, thrust on the inwall of rotating cylinder in the shape of a spiral wire arrange.
According to another embodiment of the present invention, in carbonization process, charring furnace comprises first rotating cylinder and co-axial second rotating cylinder that is positioned at outside first rotating cylinder, and high-temperature flue gas at first enters first rotating cylinder, enters second rotating cylinder then.Combustion gas is to be incorporated into the combustion unit from second rotating cylinder.
According to another embodiment of the present invention, in carbonization process, high-temperature flue gas and powdered carbon raw material counter current contact, promptly the flow direction of high-temperature flue gas is opposite with the translational motion direction of powdered carbon raw material.
According to another embodiment of the present invention, in carbonization process, high-temperature flue gas contacts with the following current of powdered carbon raw material, and promptly the flow direction of high-temperature flue gas is identical with the translational motion direction of powdered carbon raw material.
According to another embodiment of the present invention, in carbonization process, heating unit is the electric heating tube that is positioned at charring furnace central axis place.
According to another embodiment of the present invention, in carbonization process, the side of first rotating cylinder and second rotating cylinder and the angle of axis are 8 °-12 °, more preferably 10 °-11 ° on this basis.
Compared with prior art, owing in the floatation process of the present invention, upwards blow bubble and particulate gas is turbulent state, thereby the better effects if of flotation, the flotation rate is higher.Utilize method of the present invention to set out, after flotation and alkali activation, prepare the super-activated carbon of high-ratio surface, high added value by flyash.
The present invention is described in further detail below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the schema of technology of the present invention;
Fig. 2 is the structured flowchart of embodiment 1 of realizing the system of the inventive method;
Fig. 3 is the structural representation of embodiment illustrated in fig. 21 floatation system;
Fig. 4 is the structural representation of embodiment illustrated in fig. 21 charing system;
Fig. 5 is the structural representation of embodiment illustrated in fig. 21 activation system;
Fig. 6 is the structural representation of floatation system of embodiment 2 of realizing the system of the inventive method.
Embodiment
As shown in Figure 1, the technology by the fly-ash Preparation gac of the present invention, comprise to fly ash grain carry out flotation process, to the powdered carbon raw material that floatingly selects carry out charing process, the powdered carbon after the charing is carried out the activatory process.
Wherein, floatation process comprises the steps:
1. in fly ash grain, add flotation agent, form first mixture;
2. in floatation equipment, make step 1. in first mixture of gained fall from top;
3. in floatation equipment, form the gas upwards blow, first mixture formation counter current contact that this gas and step fall in 2., and also this gas is turbulent state in the process that moves upward;
4. collect step 3. in the particulate matter of the flotation plate by floatation equipment upwards;
5. to step 4. in the particulate matter of gained add flotation agent, form second mixture;
6. in floatation equipment, make step 5. in second mixture of gained fall from top;
7. in floatation equipment, form the gas upwards blow, second mixture formation counter current contact that this gas and step fall in 6., and also this gas is turbulent state in the process that moves upward;
8. collect step 7. in the particulate matter of the flotation plate by floatation equipment upwards.
Carbonization process comprises the steps:
A utilizes heating unit, and the powdered carbon raw material in the rotating cylinder of charring furnace is heated, and this powdered carbon raw material produces combustible combustion gas under heat effect;
B closes heating unit;
C feeds the combustion gas that steps A produced in the combustion unit and burns, and produces high-temperature flue gas;
D feeds rotating cylinder with the high-temperature flue gas that is produced, and the powdered carbon raw material is heated, and produces combustible combustion gas;
The combustion gas that E is produced step D feeds in the combustion unit burns, and produces high-temperature flue gas;
F repeated execution of steps D and step e.
Reactivation process comprises the steps:
Powdered carbon, the refinery coke of a after with potassium hydroxide, charing mixes according to 3: 0.4: 0.6 weight ratio and stirs, and puts into activation furnace; Wherein the powdered carbon ash content weight after the charing of flyash extraction is less than 3%, and refinery coke is crushed to 80 orders;
B feeds nitrogen in activation furnace, discharge air wherein, and its temperature rise rate is: when being warming up to 150 ℃, the air in the activation furnace is discharged substantially; Adopt the method for temperature-gradient method-insulation simultaneously, be warming up to 800 ℃, it specifically divides three sections to carry out: be warming up to 400 ℃ in first section, then insulation; In second section, be warming up to 500 ℃, then insulation; In the 3rd section, be warming up to 800 ℃, then insulation;
C imports the gas that activation furnace produced and fills in the encloses container of water, carry out water seal and reclaim, and this encloses container further is provided with the pneumatic outlet after water seal is reclaimed;
D reclaims back effluent air from encloses container to water seal and filters, to remove solid particulate wherein, emptying then;
E is cooled to 140 ℃ with activation furnace, and products therefrom washs, drying, obtains the gac of high-specific surface area.
Embodiment 1
Figure 2 shows that the embodiment 1 of the system that realizes the inventive method, it utilizes the fly ash grain flotation to obtain carbon granule (powdered carbon raw material), after drying, the granulation, again it is carried out charing, and the powdered carbon after the charing activated, it comprises floatation system, charing system, activation system.
Figure 3 shows that the floatation system of present embodiment, it comprises a flotation unit, and this flotation unit comprises: storage device 11, distribution device 12, the cylindrical shell 13 that vertically is provided with, the diffusing device of air 14 of the bucket-shaped reflection of awl, multilayer flotation plate 15, air feeder 16, physical separation means such as ultrasonic wave tripping device 18, screen plate 19, tail ash bin 110, overflow collection section 1301, tail ash collection section 1305.
Vertically the cylindrical shell 13 that is provided with can be divided into three parts, is followed successively by from top to bottom: the first flotation section 1302, divergent cone section 1303, the second flotation section 1304.Wherein, the first flotation section 1302 is thinner, is provided with one deck flotation plate 15 in it.The second flotation section 1304 is thicker, is provided with loose device of air 14 and one deck flotation plate 15 in it.Divergent cone section 1303 is the bucket-shaped transitional region of the awl of point upward between the first flotation section 1302 and the second flotation section 1304.
Tail ash collection section 1305 is that the awl of pointed end is bucket-shaped, and its bottom tip place is provided with tail ash outlet 1306, tail ash outlet 1306 is connected with tail ash tube road 1307, tail ash tube road 1307 is connected to tail ash bin 110, tail ash bin 110 is positioned at the end in tail ash tube road 1307, and be enclosed within outside the tail ash tube road 1307, the height of tail ash tube road 1307 ends is positioned on the top layer flotation plate, and the end in tail ash tube road 1307 is provided with liquid level regulation apparatus, and the height that is used for the end by regulating tail ash tube road 1307 is regulated the liquid level in the flotation unit.The bottom of tail ash bin 110 is provided with ash discharging hole 1308.Between the second flotation section 1304 and tail ash collection section 1305, be provided with screen plate 19.
The device of air 14 that looses is that the awl of point upward is bucket-shaped, and its awl bucket angle is 120 °, and its conical surface is provided with a plurality of pores 1401; It is positioned at the second flotation section 1304, and is positioned at 1305 tops, awl bucket-shaped tail ash collection section.The device of air 14 that looses is provided with a plurality of ultrasonic separation means 18.
Multilayer (for example three layers) the flotation plate 15 that is provided with lays respectively in the first flotation section 1302 and the second flotation section 1304 at interval, and wherein the flotation plate 15 of bottom is positioned at the top of the bucket-shaped diffusing device of air 14 of awl.
Be provided with whipping appts 1101 in the storage device 11, be used for powdered coal ash slurry and flotation agent are fully stirred.The bottom of storage device 11 is provided with charging line 1102, and charging line 1102 is provided with slag stock pump 1103, and this charging line 1102 leads to distribution device 12.
The principle of work of this floatation system is: the main component of flyash is carbon granule and ash content.After adding flotation agent and/or collecting agent and/or other auxiliary agent, the particle in the flyash contacts, collides with bubble, and the carbon granule that flotability is good optionally adheres to bubble, and is carried rising, realizes flotation.The ash content of flotability difference is then to sinking.
Figure 4 shows that the charing system of present embodiment, it comprises for example roasting kiln 27 of charring furnace and combustion unit.Wherein charring furnace comprises the drive unit (not shown) of feeding unit 21, first rotating cylinder 22, second rotating cylinder 23, collection device 24, combustion gas-flue gas loop structure 25, heating unit 26, driving first rotating cylinder 22 and 23 rotations of second rotating cylinder.
Wherein, first rotating cylinder 22 is the cylinder of sealing, its axis horizontal, and its inwall is provided with a plurality of plate (not shown) of raising; The end face of first rotating cylinder, 22 stems is provided with first opening 2503; The side of first rotating cylinder, 22 afterbodys is provided with a plurality of second openings 2504, its all be positioned at the equidistant same vertical section of the tail end of first rotating cylinder 22 on.
Feeding unit 21 is the feed pipe 2101 that is communicated with first opening 2503; The bottom sealing of feed pipe 2101, the top is provided with opening for feed 2102; Be provided with the baffle plate 2103 that is obliquely installed, point to first opening 2503 in the feed pipe 2101; The below of the sidewall of feed pipe 2101, first opening 2503 is provided with the 5th opening 2502, the five openings 2502 and connects first gas pipeline 2501 that leads to combustion unit.
Second rotating cylinder 23 is round table-like for sealing, the dead in line of its axis and first rotating cylinder 22, and the side of second rotating cylinder 23 and the angle of axis are 10 °; Second rotating cylinder 23 is enclosed within outside first rotating cylinder 22, and a plurality of second openings 2504 of first rotating cylinder 22 are enclosed within second rotating cylinder 23; Second rotating cylinder, 23 thinner stems are close to the afterbody of first rotating cylinder 22, the stem that second rotating cylinder, 23 thicker afterbodys are close to first rotating cylinder 22; The inwall of second rotating cylinder 23 is provided with a plurality of plate (not shown) of raising.The side of second rotating cylinder, 23 afterbodys is provided with a plurality of the 3rd openings 2505, its all be positioned at the equidistant same vertical section of the tail end of second rotating cylinder 23 on.
Combustion gas-flue gas loop structure 25 comprises first gas pipeline 2501, the 5th opening 2502, first opening 2503, second opening 2504, the 3rd opening 2505, the 4th opening 2506, second gas pipeline 2507.
Roasting kiln 27 comprises gitter brick 2701, the inlet mouth 2702 that is positioned at roasting kiln 27 belows that is positioned at roasting kiln, the air outlet 2703 that is positioned at roasting kiln 27 tops.The inlet mouth 2702 of roasting kiln 27 is connected with the other end of second gas pipeline 2507, is provided with gas pump 28 in the middle of second gas pipeline 2507.The other end of first gas pipeline 2501 is connected to the air outlet 2703 of roasting kiln.
The workflow of this charing system is as follows:
1, powdered carbon raw material.Carbon granule through flotation enters feed pipe 2101 as the powdered carbon raw material from opening for feed 2102, after being stopped by baffle plate 2103, enter first rotating cylinder 22 from first opening 2503, under the driving of drive unit, first rotating cylinder 22 and 23 rotations of second rotating cylinder, the plate of raising that drive is positioned on first rotating cylinder 22 and second rotating cylinder, 23 inwalls rotates, and the direction of powdered carbon raw material to second opening 2504 pushed.In the process that the powdered carbon raw material moves ahead, contact with the heating unit 26 or the high-temperature flue gas that are positioned at first rotating cylinder 22, and be heated.The powdered carbon raw material falls into second rotating cylinder 23 from second opening 2504, and the plate of raising that is rotated pushes to the direction of the 3rd opening 2505.In whole moving process, the powdered carbon raw material is heated, dry, pyrolysis, finally by charing.Powdered carbon raw material after the charing is fallen in the collection device 24 that is enclosed within outside second rotating cylinder 23 from the 3rd opening 2505, and leaves charring furnace through discharge pipe 2401.
2, combustion gas-flue gas.Combustion gas-flue gas is that following current contacts with the powdered carbon raw material in the present embodiment.Under the heat effect of heating unit 26, powdered carbon raw material in first rotating cylinder 22 produces inflammable gas under heat effect, this inflammable gas enters second rotating cylinder 23 along the flow direction of powdered carbon raw material through second opening 2504, and entering roasting kiln 27 through the 3rd opening 2505, the 4th opening 2506, second gas pipeline 2507, the burning back produces the pyritous flue gas in roasting kiln 27.High-temperature flue gas enters first rotating cylinder 22 through first gas pipeline 2501, the 5th opening 2502, first opening 2503.Powdered carbon raw material in first rotating cylinder 22 produces inflammable gas under the heat effect of high-temperature flue gas, this inflammable gas repeats above-mentioned flow process.
Figure 5 shows that the activation system of present embodiment, it comprises activation furnace 31, nitrogen supply (NS) device 32, first retrieving arrangement 33, second retrieving arrangement 34.
Wherein, activation furnace 31 is an encloses container, is provided with material container such as nickel crucible 3101, heating unit such as many electrical heating wires 3102 in it; Its top is provided with vertical gas pipeline 3103, and gas pipeline 3103 vertical outlets are first air outlet, and this place, first air outlet is provided with explosion trap 3104, and when the violent expansion of the gas in the activation furnace surpassed certain limit, explosion trap 3104 was opened automatically.The below of the sidewall of gas pipeline 3103, first air outlet is provided with nitrogen inlet mouth 3105.The body of heater of activation furnace 31 is provided with second air outlet 3106; Place, second air outlet 3106 is connected with second connecting tube 3107; Activation furnace 31 is the intermittent type activation furnace, and its side is provided with the end cap 3108 that can open, and end cap is provided with the water cooled pipeline (not shown) that is used for logical water coolant.Activation furnace 31 is provided with the tensimeter 3109 that is used to show in the stove.Activation furnace 31 also comprises the heating control cabinet 3110 that is used to control electrical heating wire 3102, to realize accurately controlling Heating temperature and heat-up time.
Nitrogen supply (NS) device 32 is connected with the nitrogen inlet mouth 3105 of activation furnace 31 by first connecting tube 3201;
First retrieving arrangement 33 is an encloses container, is provided with absorption liquid 3306, the second connecting tubes 3107 in it and injects in first retrieving arrangement 33, and extend to below the liquid level of absorption liquid 3306; The top of absorption liquid 3306 liquid levels, the top of first retrieving arrangement 33 are provided with air outlet 3301.The bottom of first retrieving arrangement 33 is provided with first recovery channel 3303 that reclaims liquid outlet 3302 and be connected in this recovery liquid outlet 3302, and this first recovery channel 3303 is provided with valve.First retrieving arrangement 33 is provided with the water level gauge 3304 that is used for water level in the display unit, and the pressure regulator valve 3305 that is used to regulate activation furnace 31 internal pressures.
Second retrieving arrangement 34 is an encloses container, and it is provided with opening for feed 3401, material reclaims mouth 3402, venting port 3403, filtering net 3405.Opening for feed 3401 is located at the sidewall of second retrieving arrangement 34, the below of filtering net 3405, and is connected with the air outlet 3301 of first retrieving arrangement 33 by the 3rd connecting tube 3404; Material reclaims the bottom that mouth 3402 is positioned at second retrieving arrangement 34; Venting port 3403 is arranged at the top of second retrieving arrangement 34, the top of filtering net 3405.Venting port 3403 is externally connected with gas exhaust duct 3408.The length of the 3rd connecting tube 3404 is longer, and the gas in such first retrieving arrangement 33 has the adequate time cooling in the process through the 3rd connecting tube 3404.Second recovery channel 3406 is connected in material and reclaims mouth 3402, and this second recovery channel 3406 is provided with valve.
Embodiment 2
The other parts of the embodiment 2 of the system of realization the inventive method are similar to embodiment 1, and its difference is that floatation system comprises two flotation units, and second flotation unit promptly is set after first flotation unit.This second flotation unit comprises: distribution device 12 ', the cylindrical shell 13 ' that vertically is provided with, the diffusing device of air 14 ' of the bucket-shaped reflection of awl, multilayer flotation plate 15 ', air feeder 16 ', physical separation means such as ultrasonic wave tripping device 18 ', screen plate 19 ', overflow collection section 1301 ', tail ash collection section 1305 '.
Vertically the cylindrical shell 13 ' that is provided with can be divided into three parts, is followed successively by from top to bottom: the first flotation section 1302 ', divergent cone section 1303 ', the second flotation section 1304 '.Wherein, the first flotation section 1302 ' is thinner, is provided with one deck flotation plate 15 ' in it.The second flotation section 1304 ' is thicker, is provided with loose device of air 14 ' and one deck flotation plate 15 ' in it.Divergent cone section 1303 ' is positioned between the first flotation section 1302 ' and the second flotation section 1304 ', is the bucket-shaped transitional region of the awl of point upward.
Overflow collection section 1301 ' to first flotation section 1302 ' is thick, be enclosed within outside the first flotation section 1302 ', and the top of the first flotation section 1302 ' is positioned between the top and bottom of overflow collection section 1301 '; In addition, the bottom of overflow collection section 1301 ' is provided with discharge port 1309 '.
Tail ash collection section 1305 ' is that the awl of pointed end is bucket-shaped, and its bottom tip place is provided with tail ash outlet 1306 '.Between the second flotation section 1304 ' and tail ash collection section 1305 ', be provided with screen plate 19 '.
The device of air 14 ' that looses is that the awl of point upward is bucket-shaped, and its awl bucket angle is 120 °, and its conical surface is provided with a plurality of pores 1401 '; It is positioned at the second flotation section 1304 ', and is positioned at 1305 ' top, the bucket-shaped tail ash of awl collection section.The device of air 14 ' that looses is provided with a plurality of ultrasonic separation means 18 '.
Multilayer (for example two-layer) the flotation plate 15 ' that is provided with lays respectively in the first flotation section 1302 ' and the second flotation section 1304 ' at interval, and wherein the flotation plate 15 ' of bottom is positioned at the top of the bucket-shaped diffusing device of air 14 ' of awl.
Distribution device 12 ' is positioned at 1301 ' top, overflow collection section, is provided with the container of many (for example 8) distributing pipelines 1201 ' for the bottom.The end of distributing pipelines 1201 ' is positioned within the second flotation section 1304 ', bores between bucket-shaped diffusing device of air 14 ' and the bottom flotation plate 15 '.
The discharge port 1309 of first flotation unit connects discharge pipe 1701, and the other end of this discharge pipe 1701 leads to the distribution device 12 ' of second flotation unit.
Air feeder 16 ' connects first gas pipeline 1601 ' and second gas pipeline 1602 '; Wherein, first gas pipeline 1601 ' is communicated with a plurality of pores 1401 ' of awl on the bucket-shaped diffusing device of air 14 ', and second gas pipeline 1602 ' leads to distribution device 12 '.
The workflow of this floatation system can be divided into two stages: fs in first flotation unit and the subordinate phase in second flotation unit.
Wherein the fs is: the powdered coal ash slurry in storage device 11 adds flotation agent, forms mixture.The charging line 1102 of this mixture through being positioned at storage device 11 bottoms enters distribution device 12.The powdered coal ash in the distribution device 12 and many distributing pipelines 1201 of mixture through being positioned at distribution device 12 bottoms of flotation agent enter cylindrical shell.Air feeder 16 is by pore 1401 air feed in cylindrical shell on the device of air 14 that looses, carbon granule adheres to bubble under the effect of flotation agent, and scatter floating and move upward with turbulent state, smoothly by the hole on each layer flotation plate 15, fall on the flotation plate 15 of the superiors, realize the flotation of carbon granule.The ash content of flotability difference is fallen tail ash collection section 1305 then not by 15 flotation of flotation plate.The carbon granule that floatingly selects is collected in the overflow collection section 1301, and from discharge port 1309 in discharge pipe 1701 enters the distribution device 12 ' of second flotation unit, begun the subordinate phase of flotation.
Subordinate phase be that the carbon granule that floatingly selects with the fs is as the further flotation of raw material, to make the higher particle of carbon content.Its flow process and fs are similar, are specially: many distributing pipelines 1201 ' of particle through being positioned at distribution device 12 ' bottom in the distribution device 12 ' enter cylindrical shell.Air feeder 16 ' is by the pore 1401 ' air feed in cylindrical shell on the device of air 14 ' that looses, carbon granule adheres to bubble under the effect of flotation agent, and scatter floating and move upward with turbulent state, smoothly by the hole on each layer flotation plate 15 ', fall on the flotation plate 15 ' of the superiors, realize the flotation of carbon granule.The carbon granule that floatingly selects is collected in the overflow collection section 1301 '.The ash content of flotability difference is fallen tail ash collection section 1305 ' then not by the 15 ' flotation of flotation plate, and discharges from tail ash outlet 1306 '.
Though the present invention discloses as above with preferred embodiment, is not in order to limit scope of the invention process.Any those of ordinary skill in the art, promptly every when doing a little improvement in not breaking away from invention scope of the present invention according to the equal improvement that the present invention did, should be invention scope of the present invention and contain.
Claims (10)
1. technology of making gac, it comprises fly ash grain is carried out the process of flotation and the particulate state carbonaceous material that floatingly selects is carried out the activatory process;
Wherein, described floatation process comprises the steps:
1. in fly ash grain, add flotation agent, form mixture;
2. in floatation equipment, make step 1. in the mixture of gained fall from top;
3. in floatation equipment, form the gas upwards blow, the mixture formation counter current contact that this gas and step fall in 2., and also this gas is turbulent state in the process that moves upward;
4. collect step 3. in the particulate matter of the flotation plate by described floatation equipment upwards;
Described reactivation process comprises the steps:
A with potassium hydroxide, carbon dust according to 6-2: 1 weight ratio mixes, and puts into activation furnace;
B feeds nitrogen in described activation furnace, discharge air wherein, adopts the method for temperature-gradient method-insulation simultaneously, is warming up to 700 ℃-1000 ℃, preferably is warming up to 700 ℃-900 ℃;
C imports the gas that described activation furnace produced and fills in the encloses container of water, carry out water seal and reclaim, and this encloses container further is provided with the pneumatic outlet after water seal is reclaimed;
D lowers the temperature described activation furnace, and products therefrom washs, drying, obtains the gac of high-specific surface area.
2. technology as claimed in claim 1, wherein, in the described floatation process, described turbulent state is by the different multiply upward air stream of described gas angulation in described floatation equipment is formed.
3. technology as claimed in claim 1, wherein, described floatation process further comprises the steps:
5. in floatation equipment, make step 4. in the particulate matter of gained fall from top;
6. in floatation equipment, form the gas upwards blow, the particulate matter formation counter current contact that this gas and step fall in 5., and also this gas is turbulent state in the process that moves upward;
7. collect step 6. in the particulate matter of the flotation plate by described floatation equipment upwards.
4. technology as claimed in claim 1 wherein, in the described floatation process, is used ultrasonic separation means in described floatation equipment, to promote peeling off of carbon granule and ash particles.
5. technology as claimed in claim 1 wherein, in the described floatation process, is provided with plane of reflection in described floatation equipment, make mixture that falls from the top and the particle that is passed down through the flotation plate that reflection upwards take place.
6. technology as claimed in claim 1, wherein, in the described reactivation process, described carbon dust comprises particulate state carbonaceous material and the refinery coke that is obtained by the fly ash grain flotation, its weight ratio is 2: 8-8: 2, be preferably 3: 7-7: 3.
7. as claim 1 or 6 described technologies, wherein, in the described reactivation process, back effluent air from described encloses container is reclaimed in water seal filter, to remove solid particulate wherein, emptying then.
8. technology as claimed in claim 1 wherein, after described floatation process, before the described reactivation process, also comprises the process of the particulate state carbonaceous material that floatingly selects being carried out charing, and described carbonization process comprises the steps:
A utilizes heating unit, and the powdered carbon raw material in the rotating cylinder of charring furnace is heated, and this particulate state carbonaceous material produces combustible combustion gas under heat effect;
B closes described heating unit;
C feeds the combustion gas that steps A produced in the combustion unit and burns, and produces high-temperature flue gas;
D feeds described rotating cylinder with the high-temperature flue gas that is produced, and described powdered carbon raw material is heated, and produces combustible combustion gas;
The combustion gas that E is produced step D feeds in the described combustion unit burns, and produces high-temperature flue gas;
F repeated execution of steps D and step e.
9. technology as claimed in claim 8 wherein, in the described carbonization process, in the described heated while of powdered carbon raw material, is rotated described rotating cylinder, thereby described particulate state carbonaceous material is rolled.
10. technology as claimed in claim 8 wherein, in the described carbonization process, is provided with the device that drives described powdered carbon raw material motion in the described rotating cylinder.
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| CN103626174A (en) * | 2013-11-29 | 2014-03-12 | 蒋轶军 | Method for preparing coaly activated carbon by using fly ash or slag ash |
| CN104512892A (en) * | 2015-01-08 | 2015-04-15 | 劳淑仪 | Technology for preparing activated carbon through fly ash |
| CN106733208A (en) * | 2017-01-11 | 2017-05-31 | 青岛海西万润达集团有限公司 | Low ash content semi-coke and its wet flotation technique |
| CN109095467A (en) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | Active carbon and preparation method thereof |
| CN109603973A (en) * | 2018-12-04 | 2019-04-12 | 青海泰宁水泥有限公司 | Composite Portland cement preparation facilities and preparation method thereof |
| CN109622128A (en) * | 2018-12-04 | 2019-04-16 | 青海泰宁水泥有限公司 | It is exclusively used in preparing the device and preparation method of high sulfuric-resisting portland cement |
| CN109622129A (en) * | 2018-12-04 | 2019-04-16 | 青海泰宁水泥有限公司 | Prepare the device and preparation method of cement additive |
| CN113510142A (en) * | 2021-08-16 | 2021-10-19 | 中国建筑第四工程局有限公司 | Intelligent flotation device for regeneration treatment of solid waste of construction waste and flotation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626174A (en) * | 2013-11-29 | 2014-03-12 | 蒋轶军 | Method for preparing coaly activated carbon by using fly ash or slag ash |
| CN104512892A (en) * | 2015-01-08 | 2015-04-15 | 劳淑仪 | Technology for preparing activated carbon through fly ash |
| CN106733208A (en) * | 2017-01-11 | 2017-05-31 | 青岛海西万润达集团有限公司 | Low ash content semi-coke and its wet flotation technique |
| CN109095467A (en) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | Active carbon and preparation method thereof |
| CN109603973A (en) * | 2018-12-04 | 2019-04-12 | 青海泰宁水泥有限公司 | Composite Portland cement preparation facilities and preparation method thereof |
| CN109622128A (en) * | 2018-12-04 | 2019-04-16 | 青海泰宁水泥有限公司 | It is exclusively used in preparing the device and preparation method of high sulfuric-resisting portland cement |
| CN109622129A (en) * | 2018-12-04 | 2019-04-16 | 青海泰宁水泥有限公司 | Prepare the device and preparation method of cement additive |
| CN113510142A (en) * | 2021-08-16 | 2021-10-19 | 中国建筑第四工程局有限公司 | Intelligent flotation device for regeneration treatment of solid waste of construction waste and flotation method thereof |
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Application publication date: 20111123 |