CN106315597B - A kind of method and device that the integrated treatment of flyash utilizes - Google Patents
A kind of method and device that the integrated treatment of flyash utilizes Download PDFInfo
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- CN106315597B CN106315597B CN201610703692.5A CN201610703692A CN106315597B CN 106315597 B CN106315597 B CN 106315597B CN 201610703692 A CN201610703692 A CN 201610703692A CN 106315597 B CN106315597 B CN 106315597B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention provides the methods that a kind of integrated treatment of flyash utilizes, comprising the following steps: uses magnetic separator iron removal by magnetic separation after grinding flyash again；Material after grinding is handled using hot acid liquid, it is spare after washing, dehydration；Fluorine-containing acid solution is added into reaction kettle under stirring conditions, and hydrochloric acid and/or nitric acid, material is put into reaction kettle, reaction generates silicon tetrafluoride gas, and silicon tetrafluoride gas is brought into cooling reactor together with the sour gas and vapor that are volatilized in mix acid liquor by negative pressure；Mixed gas is reacted in cooling reactor generates SiO2·nH2O collects the SiO in cooling reactor2·nH2O removes wherein remaining sour gas, can be prepared by fumed silica product after dry.The present invention additionally provides a kind of device in the above method simultaneously.The present invention is prepared into the product gas phase silica of high added value using wastes such as flyash as raw material, therefore has achieved the effect that turn waste into wealth.
Description
Technical field
The present invention relates to a kind of coal-burning power plant's wastes --- and the method and device that the integrated treatment of flyash utilizes belongs to
Chemical industry purification and environmental technology field.
Background technique
According to Yang Jing, Jiang Zhouqing, Ma Hongwen, Su Shuanqing, Wang Mingwei, Li Jinhong, Yao Wengui etc. are in " aluminum resources and high alumina
Flyash extracts aluminium oxide progress " it introduces in a text: flyash is clay mineral in fire coal and associated mineral in high temperature
Under calcined product, the chemical component of flyash is mainly the silicates and oxides of silicon, aluminium, iron, calcium.According to statistics, 2004
Year, Coal Ash in China discharge amount was more than 200,000,000 tons, and flyash discharge capacity in 2010 is 4.8 hundred million tons, it is contemplated that flyash discharge in 2015
Amount will be up to 5.8 hundred million tons, and discharge pile over the years has 2,500,000,000 tons or more of flyash of grey field, resulting land occupation and environment in addition
Pollution problem is very prominent.Currently, flyash is mainly used for the fields such as construction material and construction project, silicate cement is such as produced
Mud, concrete, autoclaved fly ash brick, filler etc..
The raw material that vapor phase method prepares silica is generally silicon tetrachloride, oxygen (or air) and hydrogen, reacts under high temperature
It forms.Its chemical equation are as follows: SiCl4+2H2+O2—>SiO2+ 4HCl, silicon tetrachloride gasify (flame temperature 1000 at high temperature
~1800 DEG C) after, vapor phase hydrolysis is carried out at a high temperature of 1800 DEG C or so with a certain amount of hydrogen and oxygen (or air)；It generates at this time
Vapor phase process silica particles it is superfine, with gas formed aerosol, be not easy to trap, thus make its elder generation be gathered into collector compared with
Bulky grain is re-fed into deacidification furnace then through cyclone collection, is 4 with nitrogenous air blowing fumed silica to pH value
~6 be finished product.The enterprise that China produces fumed silica at present mostly uses this method, which is also gas general in the world
The production method of aerosil.Ye You enterprise, China produces fumed silica using methyl trichlorosilane, and successfully complete
At industrialized production.There is only high-temperature process in the production technology of fumed silica now, but also use non-
Often dangerous and inflammable and explosive hydrogen and oxygen, the operating environment of worker is arduouser in production process；To safety coefficient
It is required that very high.Related data and Chinese patent literature are consulted, does not find the phase using other raw materials production fumed silica
Close report.
If secondary operation utilization can be carried out flyash, it is combined with the preparation of fumed silica, is used for
Fumed silica product is prepared, then there is significant progress by above-mentioned two intractable technical problem in this field is solved.
Summary of the invention
The present invention provides the method that a kind of integrated treatment of flyash utilizes, this method successfully, is creatively avoided
Vapor phase method prepares the technical process that hydrogen and oxygen and pyrohydrolysis are used during fumed silica now, and the present invention is same
When additionally provide and can produce fumed silica product and process units under room temperature tiny structure.
Realize technical solution used by above-mentioned purpose of the present invention are as follows:
A kind of method that the integrated treatment of flyash utilizes, comprising the following steps: (1) it is small, by flyash to be ground to partial size
In 200 meshes, then with magnetic separator iron removal by magnetic separation, the content of each ingredient therein is then analyzed；
(2), by the material after grinding using hot acid liquid handle, it is molten remove metal oxide therein, remove acid solution and wash,
Spare after dehydration, the acid solution is the mix acid liquor of one or more of hydrochloric acid, nitric acid and sulfuric acid；
(3), fluorine-containing acid solution and hydrochloric acid and/or nitric acid, the fluoric-containing acid is added into reaction kettle under stirring conditions
Liquid is hydrofluoric acid and/or fluosilicic acid, opens cooling device and exhaust gas absorption device in reaction system, will be made in step (2)
Material investment reaction kettle in, lasting stirring during feeding intake, controlling the reaction temperature in reaction kettle is 70~95 DEG C, fluoric-containing acid
The silicon dioxde reaction in hydrofluoric acid or fluosilicic acid and material in liquid generates silicon tetrafluoride gas, which is dissolved in instead
Formation fluosilicic acid in the water of system is answered to continue to dissolve the silica in flyash, another part silicon tetrafluoride gas and mixed acid
The sour gas and vapor to be volatilized in liquid is brought into cooling reactor by negative pressure together；
(4), control cooling reactor in cooling temperature be 10~36 DEG C, mixed gas react in cooling reactor generation HF,
Cl2/NO2、SiO2·nH2O, wherein HF and Cl2/NO2It is taken out of from cooling reactor by negative pressure, and is only absorbed by the water generation for repeating to make
Hydrofluoric acid, hydrochloric acid/nitric acid, SiO2·nH2On the cooling device that O condensation is adsorbed in cooling reactor, collect in cooling reactor
SiO2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein remaining acidity
Gas HF and Cl2/NO2, then it is dried again, can be prepared by fumed silica product, SiO in product after dry2Content is big
In 99.9%, multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), it is filtered after the reaction was completed in reaction kettle, obtains filter residue and filtrate, filtrate is reused after purification.
First flyash is activated at 750~950 DEG C before the grinding in step (1), grinding using wet grinding mill or
Person's dry method mill.
The acid solution collection after removing is handled in step (2), recycles valuable metal therein or preparation aluminium salt product, such as:
Aluminum sulfate, aluminium polychloride etc..
In mix acid liquor described in hot acid liquid described in step (2) and step (3), the mass concentration or volume of hydrofluoric acid
Concentration is 10~40%, and the mass concentration or volumetric concentration of fluosilicic acid are 10~30%, the mass concentration or volumetric concentration of nitric acid
It is 10~20%, the mass concentration or volumetric concentration of hydrochloric acid are 10%~30%, and the mass concentration or volumetric concentration of sulfuric acid are
10%~40%.
Described device includes that hot-air is sent into system, chemical reaction system, cooling system and waste gas absorbing system, wherein
Hot-air be sent into system for storing compressed air and be sent into after being heated to air chemical reaction system and in；The chemistry
Reaction system is made of acid solution storage tank, feed bin and reaction kettle, and the bottom of acid solution storage tank and feed bin is connected by pipeline with reaction kettle
It is logical, agitating device is provided in reaction kettle, the liner of reaction kettle is heatproof, acidproof, wear-resistant material, in the upper of reactor bottom
Side, equipped with an annular round tube, is evenly distributed with air hole or permeability cell, one or more is provided in reaction kettle on round tube
The vertical tube being connected with the round tube of annular, the pipe valve on kettle cover that the top of the vertical tube passes through reaction kettle is sent into hot-air is
System is connected；Kettle inner wall is equipped with tetrafluoro bundle of capillary tubes that be close to kettle wall and helically linear from top to bottom or from bottom to top,
The upper and lower ends of the tube bank are connect with the cold and hot medium outside kettle wall by its valve respectively, by being passed through to the capillary in tube bank
Cold and hot medium is provided for reaction system in kettle and is heated or cooled；
Cooling system is composed in series by level-one cooling reactor and second level cooling reactor；Wherein level-one cooling reactor is connected with reaction kettle
It connecing, the kettle cover of reaction kettle is equipped with a pipeline for being connected with level-one cooling reactor and being deep into level-one cooling reactor bottom center, and one
Grade cooling reactor is internally provided with cooling device, and the bottom of level-one cooling reactor is provided with outlet valve, on the kettle cover of level-one cooling reactor
It is provided with the pipeline for being connected with second level cooling reactor and being deep into second level cooling reactor bottom center, the second level cooling reactor
It is internally provided with cooling device, the bottom of second level cooling reactor is provided with outlet valve；One is provided on the kettle cover of second level cooling reactor
The pipeline being connected with waste gas absorbing system, the waste gas absorbing system are inhaled by more than one negative pressure water tourie and acid mist
Receiving apparatus forms, and pipeline is provided at the top of negative pressure water tourie and is connected by pipeline with the air-introduced machine in acid mist absorbing device
It connects.
It includes air compressor, air storage tank, air heater and pipeline, air pressure that the hot-air, which is sent into system,
Contracting machine, air storage tank and air heater are connected by pipeline, and valve and instrument are additionally provided on pipeline.
It is 10~20mm's and towards different permeability cells, adjacent permeability cell that diameter is evenly distributed on the round tube
Between spacing be 50~150mm, and the angle between the stretching direction of adjacent permeability cell is 60~120 °, is set in reaction kettle
Two vertical tubes are equipped with, two vertical tubes are connected to the left and right ends of round tube.
The cooling device of the level-one cooling reactor is made of shaft and cooling disk, and the shaft is that an outside is enclosed with
The hollow circular-tube of polytetrafluoroethylene (PTFE), the top of shaft are stretched out on the kettle cover by level-one cooling reactor, and one is provided in shaft from upper
The top of cooling water pipe A under and, cooling water pipe A are water inlet end and water inlet end is connected with cooling water source；Uniformly divide in shaft
It is furnished with cooling disk, the cooling disk is fixed in shaft by the center of circle of shaft, and is rotated with shaft, the cooling circle
Disk is hollow structure, and the inside of all cooling disks is provided with the cooling water pipe B of distribution in spiral shape, and neighbouring cold
But the cooling water pipe B in disk joins end to end, the water inlet end and cooling water pipe A of the cooling water pipe B in the cooling disk of bottommost
Bottom end be connected, lead to hollow circular-tube for the water outlet of the cooling water pipe B in the cooling disk of top, arranges in cooling water pipe B
Cooling water out is overflowed by the top of shaft；It is evenly distributed with vertical venthole on the cooling disk, and neighbouring
Cooling disk on venthole mutual dislocation.
The kettle cover of the level-one cooling reactor is equipped with the manhole of vacuum meter and easy access, on the kettle cover of level-one cooling reactor
It is additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.
Cooling device in the second level cooling reactor is multilayer fin structure, is provided on the kettle wall of second level cooling reactor cold
But water inlet and cooling water outlet, cooling water inlet are connected with the water inlet of lowest level fin, and cooling water is by undermost wing
Piece flows into, and the fin is in continuous bending structure, and the end of adjacent upper layer and lower layer fin is connected, cooling water outlet with it is most upper
The water outlet of layer fin is connected；Compressed air blowning installation is provided on the kettle cover of second level cooling reactor, compressed air, which is blown, to be filled
It sets and is connected with compressed gas source, the kettle cover of second level cooling reactor is equipped with vacuum meter, and its kettle cover and bottom are designed with convenient for inspection
The manhole repaired.
Compared with prior art, the technical scheme provided by the invention has the following advantages: the 1, present invention is with flyash etc.
Waste is prepared into the product gas phase silica of high added value, SiO in obtained product as raw material2Content is big
In 99.9%, multiple spot BET method measurement the specific area is not less than 350m2/ g, therefore achieved the effect that turn waste into wealth.2, this hair
Preparation process provided by bright belongs to a kind of completely new technique thinking, solves institute in existing fumed silica preparation process
Existing high-temperature process uses the disadvantages of breakneck inflammable and explosive hydrogen and oxygen.Production work provided by the present invention
Artistic skill is enough to be prepared at normal temperatures and pressures.3, in preparation process of the invention generated sour gas through negative pressure water tourie
After absorption, corresponding acid solution can be made, can be recycled, can greatly save after acid solution is concentrated to certain concentration
The problem of cost and environmental protection treatment waste water in production.4, process units provided by the invention can be realized large-scale industry metaplasia
It produces, and used components are chemical plant common tool, it is low in cost.
Detailed description of the invention
Fig. 1 is the overall structure diagram of preparation facilities provided by the invention；
Fig. 2 is the structural schematic diagram of cooling disk in level-one cooling reactor；
Fig. 3 is the structural schematic diagram of fin in second level cooling reactor；
In figure: 1- acid solution storage tank, 2- feed bin, 3- reaction kettle, 4- agitating device, 5- round tube, 6- vertical tube, 7- level-one are cooling
Kettle, 8- second level cooling reactor, 9- outlet valve, 10- negative pressure water tourie, 11- acid mist absorbing device, 12- air compressor, 13- are empty
Gas holding vessel, 14- air heater, 15- shaft, the cooling disk of 16-, 17- cooling water pipe A, 18- venthole, 19- fin.
Specific embodiment
With reference to the accompanying drawing and specific embodiment does detailed specific description to the present invention, but protection scope of the present invention
It is not limited to following embodiment.
The structure of preparation facilities provided in the present embodiment as shown in Figure 1, described device include hot-air be sent into system,
Chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air is sent into system for storing compressed air and right
Air is sent into chemical reaction system after being heated, and it includes air compressor 12, air storage that the hot-air, which is sent into system,
Tank 13, air heater 14 and pipeline are deposited, air compressor 12, air storage tank 13 and air heater 14 pass through pipeline phase
It connects, is additionally provided with valve and instrument on pipeline.
The chemical reaction system is made of acid solution storage tank 1, feed bin 2 and reaction kettle 3, the bottom of acid solution storage tank 1 and feed bin 2
It is connected by pipeline with reaction kettle 3, is provided with agitating device 4 in reaction kettle 3, the liner of reaction kettle is heatproof, acidproof, wear-resisting
Material specifically selects silicon carbide, fluorine material, graphite material etc..At the top 200mm of 3 bottom of reaction kettle or so place, it is equipped with one
The round tube 5 of annular, the diameter of the round tube are 100~200mm, and it is 10~20mm that diameter is evenly distributed on the round tube 5
And towards different permeability cells, the spacing between adjacent permeability cell is 50~150mm, and the stretching side of adjacent permeability cell
Angle between is 60~120 °.Two vertical tubes 6 being connected with the round tube of annular, two vertical tubes 6 are provided in reaction kettle
The left and right ends of round tube 5 are connected to, the pipe valve and hot-air feeding on kettle cover that the top of the vertical tube 6 passes through reaction kettle
System is connected.Kettle wall in reaction kettle has spiral hook, is used to support the polytetrafluoroethylene (PTFE) in kettle for heating or cooling down
Bundle of capillary tubes.
Cooling system is composed in series by level-one cooling reactor 7 and second level cooling reactor 8；Wherein level-one cooling reactor 7 and 3 phase of reaction kettle
The kettle cover of connection, reaction kettle 3 is equipped with a pipe for being connected with level-one cooling reactor 7 and being deep into level-one cooling reactor bottom center
Road, level-one cooling reactor 7 are internally provided with cooling device, and the cooling device of the level-one cooling reactor is by shaft 15 and cooling disk
16 compositions, the shaft 15 are the hollow circular-tube that an outside is enclosed with polytetrafluoroethylene (PTFE), and the top of shaft is by level-one cooling reactor
Kettle cover on stretch out, be provided with a top-down cooling water pipe A17 in shaft, the top of cooling water pipe A be water inlet end and
Water inlet end is connected with cooling water source；Cooling disk 16 is evenly distributed in shaft 15.The structure of cooling disk as shown in Fig. 2,
The cooling disk 16 is that the center of circle is fixed in shaft, and is rotated with shaft with shaft 15, and the cooling disk is hollow
Structure, the inside of all cooling disks are provided with the cooling water pipe B of distribution in spiral shape, and in neighbouring cooling disk
Cooling water pipe B join end to end, the bottom end phase of the water inlet end and cooling water pipe A of the cooling water pipe B in the cooling disk of bottommost
It is connected to, hollow circular-tube, the cooling being discharged in cooling water pipe B are led in the water outlet of the cooling water pipe B in the cooling disk of top
Water is overflowed by the top of shaft.Vertical venthole 18, and neighbouring cooling are evenly distributed on the cooling disk
Venthole mutual dislocation on disk, to guarantee the cooling effect of its gas.The diameter of the venthole is 10~20mm, adjacent
Venthole between center away from for 20mm~30mm.
The kettle cover of the level-one cooling reactor is equipped with the manhole of vacuum meter and easy access, on the kettle cover of level-one cooling reactor
It is additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.The kettle cover of level-one cooling reactor 7
On be provided with the pipeline for being connected with second level cooling reactor 8 and being deep into 8 bottom center of second level cooling reactor.The bottom of level-one cooling reactor
Portion is provided with outlet valve 9.
The second level cooling reactor 8 is internally provided with cooling device, and the cooling device in the second level cooling reactor is
Multilayer fin structure, is provided with cooling water inlet and cooling water outlet on the kettle wall of second level cooling reactor 8, cooling water inlet with it is most lower
The water inlet of layer fin is connected, and cooling water is flowed by undermost fin, and the fin 19 is in continuous bending structure, structure
As shown in Figure 3.The end of adjacent upper layer and lower layer fin is connected, and cooling water outlet is connected with the water outlet of top layer's fin
Logical, cooling water enters from lowest level fin, flows out to one layer of fin topmost.Compression is provided on the kettle cover of second level cooling reactor
Air puff device, compressed air blowning installation are connected with compressed gas source, compressed air purging when discharging.Second level is cooling
The kettle cover of kettle is equipped with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.The bottom of second level cooling reactor is arranged
There is outlet valve 9；The pipeline being connected with waste gas absorbing system is provided on the kettle cover of second level cooling reactor 8.
The waste gas absorbing system is made of two negative pressure water touries 10 and acid mist absorbing device 11, two negative pressure water
Tourie is connected in series or is connected in parallel.Pipeline is provided at the top of negative pressure water tourie and by pipeline and acid mist absorbing device
Air-introduced machine be connected.Acid mist after the absorption of second level water tourie occurs in acid mist absorbing device with the droplet of liquid alkaline solution
It is discharged into air again after neutralization reaction, workshop circulation is given after the concentration that the acid solution of negative pressure water tourie reaches certain to be made
With.
It elaborates by taking the produced flyash of certain power plant as an example to detailed treatment process of the invention below.Specifically
Treatment process is as follows:
(1), first flyash is activated at 750~950 DEG C, flyash is then ground to partial size less than 200 again
Mesh, grinding is ground using wet grinding mill or dry method, by drying materials after then grinding according to wet grinding mill.Then magnetic separation is used again
Then machine iron removal by magnetic separation analyzes SiO therein2、TiO2、Al2O3、Fe2O3、MgO、CaO、K2O、Na2The content of O.
(2), the material after grinding is handled using hot acid liquid, it is molten except in material to the maximum extent under heating conditions
Al2O3、Fe2O3、TiO2、MgO、CaO、K2O、Na2Spare after O, spare after removing acid solution and washing, be dehydrated, the acid solution is
The mix acid liquor of one or more of hydrochloric acid, nitric acid and sulfuric acid, select in the present embodiment mass concentration be 10%~
30% hydrochloric acid.It is individually handled again after acid solution after removing is collected, is used to prepare aluminium polychloride product.
(3), fluorine-containing acid solution and hydrochloric acid and/or nitric acid, the fluoric-containing acid is added into reaction kettle under stirring conditions
Liquid is hydrofluoric acid and/or fluosilicic acid, both can first add hydrofluoric acid and/or fluosilicic acid in the present invention, then add hydrochloric acid and/or nitre
Acid adds together after can also mixing the above acid solution.The cooling device and exhaust gas absorption device being then turned in reaction system,
Material obtained in step (2) is put into reaction kettle, lasting stirring during feeding intake.
If the fluorine-containing acid solution being added is hydrofluoric acid, since it and silicon dioxde reaction process are an exothermic process, then
70~95 DEG C of cooling water valve maintaining reaction temperature outside reaction response kettle need to be opened.If do not contained in the mix acid liquor of investment
Hydrofluoric acid and contain fluosilicic acid, then need open reacting kettle jacketing steam slowly heated to reaction kettle.Hydrogen fluorine in fluorine-containing acid solution
Silicon dioxde reaction in acid or fluosilicic acid and material generates silicon tetrafluoride gas, which is dissolved in the water of reaction system
The middle silica formed in the flyash after fluosilicic acid continues dissolution purification, another part silicon tetrafluoride gas and mix acid liquor
Middle volatilized sour gas and vapor are brought into cooling reactor by negative pressure together.Hydrofluoric acid employed in the present embodiment
Mass concentration or volumetric concentration are 10~40%, and the mass concentration or volumetric concentration of fluosilicic acid are 10~30%, the quality of nitric acid
Concentration or volumetric concentration are 10~20%, and the mass concentration or volumetric concentration of hydrochloric acid are 10%~30%, the mass concentration of sulfuric acid
Or volumetric concentration is 10%~40%.
(4), control cooling reactor in cooling temperature be 10~36 DEG C, mixed gas react in cooling reactor generation HF,
Cl2/NO2、SiO2·nH2O, chemical equation are as follows:
SiF4+4HNO3+nH2O=4HF ↑+4NO2↑+SiO2·nH2O+O2↑
2SiF4+8HCl+2O2+nH2O=8HF ↑+4Cl2+2SiO2·nH2O
Wherein HF and Cl2/NO2It is taken out of from level-one cooling reactor and second level cooling reactor by negative pressure, simultaneously into waste gas absorbing system
It is only absorbed by the water hydrofluoric acid, the hydrochloric acid/nitric acid generated for reuse, the hydrofluoric acid, hydrochloric acid/nitric acid are concentrated to certain concentration
After can be recycled；The problem of greatly having saved the cost and environmental protection treatment waste water in production in this way.
And SiO2·nH2O slowly condenses on the cooling disk being adsorbed in level-one cooling reactor, from beginning on cooling disk
Cohesion, then knot is in glittering and translucent spherical particle naturally at leisure, is flocked together as fish-egg, it is very beautiful, when level-one is cold
But when the cooling disk of kettle gathers a certain amount, opening of rotary shaft device, shaft drives cooling disc rotary, in the work of centrifugal force
Under, material is thrown to kettle wall, then the bottom of level-one cooling reactor is blown to compressed air, and the outlet valve through bottom is sent to drying
Process；After the material for having handled level-one cooling reactor, second level cooling reactor then directly opens compressed air valve, directly the object of condensation
The outlet valve through bottom is sent to drying process after material blows to bottom.
It (5), is in acidity since material contains moisture, and the volatilization of hydrofluoric acid, ocratation and nitric acid or HCl gas
Property is extremely strong, therefore before it is dried, first by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein
Remaining sour gas HF and Cl2/NO2, then it is dried again, can be prepared by fumed silica product after dry, in product
SiO2Content is greater than 99.9%, and multiple spot BET method measurement the specific area is not less than 350m2/g。
(6), due to the mix acid liquor in above-mentioned reaction be it is excessive, the silicon dioxde reaction in flyash is very complete, instead
The acid solution that the material in kettle is mainly tiny carbon particle and surplus should be remained afterwards, filtered while hot, filtered acid solution is by pure
After change, re-use；The soot particulate matter filtered out after tap water rinse, then is washed till neutrality, after dehydration and purification, spends
Ion water washing 3 times, after dehydration, drying, packaging is the charcoal particulate matter of high-purity.
Claims (1)
1. the device in a kind of comprehensive treatment utilization method for flyash, the described method comprises the following steps: (1), by powder
Coal ash is ground to partial size less than 200 meshes, then with magnetic separator iron removal by magnetic separation, then analyzes the content of each ingredient therein；
(2), the material after grinding is handled using hot acid liquid, it is molten to remove metal oxide therein, it removes acid solution and washs, is dehydrated
Spare afterwards, the acid solution is the mix acid liquor of one or more of hydrochloric acid, nitric acid and sulfuric acid；
(3), fluorine-containing acid solution and hydrochloric acid and/or nitric acid is added into reaction kettle under stirring conditions, the fluorine-containing acid solution is
Hydrofluoric acid and/or fluosilicic acid open cooling device and exhaust gas absorption device in reaction system, by object obtained in step (2)
In material investment reaction kettle, lasting stirring during feeding intake, controlling the reaction temperature in reaction kettle is 70~95 DEG C, in fluorine-containing acid solution
Hydrofluoric acid or fluosilicic acid and material in silicon dioxde reaction generate silicon tetrafluoride gas, which is dissolved in reactant
Fluosilicic acid is formed in the water of system and continues to dissolve the silica in flyash, in another part silicon tetrafluoride gas and mix acid liquor
The sour gas and vapor to be volatilized is brought into cooling reactor by negative pressure together；
(4), controlling the cooling temperature in cooling reactor is 10~36 DEG C, and mixed gas is reacted in cooling reactor generates HF, Cl2/NO2、
SiO2·nH2O, wherein HF and Cl2/NO2It is taken out of from cooling reactor by negative pressure, and is only absorbed by the water the hydrogen generated for reuse
Fluoric acid, hydrochloric acid/nitric acid, SiO2·nH2On the cooling device that O condensation is adsorbed in cooling reactor, the SiO in cooling reactor is collected2·
nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein remaining sour gas
HF and Cl2/NO2, then it is dried again, can be prepared by gas-phase silica product, SiO in product after dry2Content is greater than
99.9%, multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), it is filtered after the reaction was completed in reaction kettle, obtains filter residue and filtrate, filtrate is reused after purification；
It is characterized by: described device includes that hot-air is sent into system, chemical reaction system, cooling system and waste gas absorption system
System, wherein hot-air is sent into system and is used for storing compressed air and is sent into chemical reaction system after heating to air；Institute
Chemical reaction system is stated to be made of acid solution storage tank, feed bin and reaction kettle, the bottom of acid solution storage tank and feed bin by pipeline with react
Kettle is connected, and agitating device is provided in reaction kettle, the liner of reaction kettle is heatproof, acidproof, wear-resistant material, in reactor bottom
Top air hole or permeability cell are evenly distributed on round tube equipped with an annular round tube, be provided in reaction kettle one with
On the vertical tube that is connected of round tube with annular, the pipe valve on kettle cover that the top of the vertical tube passes through reaction kettle send with hot-air
Enter system to be connected；Kettle inner wall is equipped with tetrafluoro capillary that be close to kettle wall and helically linear from top to bottom or from bottom to top
Beam, the upper and lower ends of the tube bank are connect with the cold and hot medium outside kettle wall by its valve respectively, by the capillary in tube bank
It is passed through cold and hot medium, provides and is heated or cooled for reaction system in kettle；
Cooling system is composed in series by level-one cooling reactor and second level cooling reactor；Wherein level-one cooling reactor is connected with reaction kettle, instead
The kettle cover of kettle is answered to be equipped with a pipeline for being connected with level-one cooling reactor and being deep into level-one cooling reactor bottom center, level-one is cooling
Kettle is internally provided with cooling device, and the bottom of level-one cooling reactor is provided with outlet valve, is provided on the kettle cover of level-one cooling reactor
The inside of a piece pipeline for being connected with second level cooling reactor and being deep into second level cooling reactor bottom center, the second level cooling reactor is set
It is equipped with cooling device, the bottom of second level cooling reactor is provided with outlet valve；One and exhaust gas are provided on the kettle cover of second level cooling reactor
The pipeline that absorption system is connected, the waste gas absorbing system is by more than one negative pressure water tourie and acid mist absorbing device
It forms, be provided with pipeline at the top of negative pressure water tourie and be connected by pipeline with the air-introduced machine in acid mist absorbing device；
It includes air compressor, air storage tank, air heater and pipeline, air compression that the hot-air, which is sent into system,
Machine, air storage tank and air heater are connected by pipeline, and valve and instrument are additionally provided on pipeline；
It is 10~20mm's and towards different permeability cells that diameter is evenly distributed on the round tube, between adjacent permeability cell
Spacing be 50~150mm, and the angle between the stretching direction of adjacent permeability cell is 60~120 °, is provided in reaction kettle
Two vertical tubes, two vertical tubes are connected to the left and right ends of round tube.
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| CN102001686A (en) * | 2010-12-01 | 2011-04-06 | 陈锋 | Process for producing potassium fluoride and white carbon black by decomposing potassium feldspar with fluorine-containing acid at low temperature |
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| CN1143716C (en) * | 2001-02-28 | 2004-03-31 | 黄晸 | Differential crystallization method able to control gradient field and its equipment and application |
| CN1915811A (en) * | 2006-09-04 | 2007-02-21 | 江苏大学 | Method for preparing Nano carbon white from fly ash based on gas phase sol gel method |
| CN101214961B (en) * | 2007-12-30 | 2011-03-30 | 薛彦辉 | Method for preparing white carbon black, coal powder and aluminum hydroxide from fly ash |
| CN101746763A (en) * | 2008-12-02 | 2010-06-23 | 上海科王新型材料研究中心 | Method for preparing nano silicon dioxide by vapor phase process |
| CN101596438B (en) * | 2009-07-10 | 2011-11-30 | 浙江大学 | Adjustable biaxial reaction kettle for stirring variable physical property medium |
| CN201871355U (en) * | 2010-08-10 | 2011-06-22 | 中国石油化工股份有限公司 | High-concentration slurry heating equipment |
| CN102701221B (en) * | 2012-05-22 | 2014-02-19 | 韩钊武 | Method for preparing nano white carbon black from coal gangue |
| CN102921356B (en) * | 2012-10-22 | 2014-05-21 | 江苏华泰重工装备有限公司 | Novel esterification pre-reactor |
| CN203155179U (en) * | 2013-04-12 | 2013-08-28 | 冀州市中意复合材料有限公司 | Agitator tank for mixing materials |
| CN103420383B (en) * | 2013-07-29 | 2015-12-23 | 中国化学赛鼎宁波工程有限公司 | Take phosphatic fertilizer by-product fluosilicate as the method that raw material prepares thermal silica and anhydrous hydrofluoric acid |
| CN103663474B (en) * | 2013-12-20 | 2016-05-18 | 瓮福（集团）有限责任公司 | A kind of method of fluorine-containing Preparation of White Silica by Silica Residue |
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