CN106315597A - Fly ash comprehensive treatment and utilization method and device - Google Patents
Fly ash comprehensive treatment and utilization method and device Download PDFInfo
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- CN106315597A CN106315597A CN201610703692.5A CN201610703692A CN106315597A CN 106315597 A CN106315597 A CN 106315597A CN 201610703692 A CN201610703692 A CN 201610703692A CN 106315597 A CN106315597 A CN 106315597A
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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 invention provides a fly ash comprehensive treatment and utilization method which comprises the following steps: grinding fly ash, and carrying out magnetic separation by a magnetic separator to remove iron; treating the ground material with a hot acid solution, washing, and dewatering for later use; adding a fluorine-containing acid solution into a reaction kettle while stirring, adding hydrochloric acid and/or nitric acid into the reaction kettle, and reacting to generate silicon tetrafluoride gas, wherein the silicon tetrafluoride gas and volatile acidic gas in the mixed acid solution are taken into a cooling kettle along with vapor by negative pressure; carrying out reaction on the gas mixture in the cooling kettle to generate SiO2.nH2O, collecting the SiO2.nH2O in the cooling kettle, removing the residual acidic gas, and drying to obtain the gas-phase silicon dioxide product. The invention also provides a device used in the method. The fly ash and other wastes used as the raw materials are made into the high-added-value product gas-phase silicon dioxide, thereby achieving the effect of changing wastes into valuable substances.
Description
Technical field
The present invention relates to the method and device that the integrated treatment of a kind of coal-burning power plant waste coal ash utilizes, belong to
Chemical industry purifies and environmental technology field.
Background technology
According to Yang Jing, Jiang Zhouqing, horse great writing, Su Shuanqing, Wang Mingwei, Li Jinhong, Yao Wengui etc. are at " aluminum resources and high alumina
Flyash extracts aluminium oxide progress " literary composition to be introduced: flyash is that the clay mineral in fire coal and associated mineral are at high temperature
Product after lower calcining, the chemical composition of flyash is mainly the silicates and oxides of silicon, aluminum, ferrum, calcium.According to statistics, 2004
Year, Coal Ash in China discharge capacity was more than 200,000,000 tons, and within 2010, flyash discharge capacity is 4.8 hundred million tons, it is contemplated that flyash discharge in 2015
Amount will reach 5.8 hundred million tons, in addition the flyash of more than 2,500,000,000 tons of discharge pile existence ash field over the years, consequent occupation of land and environment
Pollution problem is the most prominent.At present, flyash is mainly used in the field such as construction material and construction project, as produced silicate cement
Mud, concrete, autoclaved fly ash brick, filler etc..
Vapor phase method is prepared the raw material of silicon dioxide and is generally Silicon chloride., oxygen (or air) and hydrogen, reacts under high temperature
Form.Its chemical equation is: SiCl4+2H2+O2—>SiO2+ 4HCl, Silicon chloride. at high temperature gasifies (flame temperature 1000
～1800 DEG C) after, under the high temperature of about 1800 DEG C, carry out vapor phase hydrolysis with a certain amount of hydrogen and oxygen (or air)；Now generate
Vapor phase process silica particles superfine, form aerosol with gas, be difficult to trapping, therefore make it first be gathered into relatively in collector
Bulky grain, then through cyclone collection, is re-fed into deacidification furnace, is 4 with nitrogenous air blowing aerosil to pH value
～6 be finished product.China produces the enterprise of aerosil at present and mostly uses this method, and this method is also the most general gas
The production method of aerosil.Ye You enterprise of China uses methyl trichlorosilane to produce aerosil, and the completeest
Become industrialized production.The production technology of fumed silica now does not only exist high-temperature process, but also uses non-
Often dangerous and inflammable and explosive hydrogen and oxygen, in its production process, the operating environment of workman is arduouser；To safety coefficient
Require the highest.Consult related data and Chinese patent literature, do not find to utilize the phase of other raw material production aerosils
Close report.
If flyash can be carried out secondary operations utilization, it is combined with the preparation of aerosil, is used for
Prepare aerosil product, then the thorny technical problem of above-mentioned two in this area will be solved, have the most progressive.
Summary of the invention
The invention provides the method that the integrated treatment of a kind of flyash utilizes, the method is successfully, creatively avoid
Use hydrogen and oxygen and the technical process of pyrohydrolysis during vapor phase method prepares aerosil now, the present invention with
Time additionally provide and can produce aerosil product and process units under room temperature tiny structure.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
The method that the integrated treatment of a kind of flyash utilizes, comprises the following steps: (1), that flyash is ground to particle diameter is little
In 200 mesh sieves, then use magnetic separator iron removal by magnetic separation, then analyze the content of wherein each composition；
(2), will grind after material use hot acid liquid to process, molten except metal-oxide therein, removing acid solution and wash,
After dehydration standby, described acid solution is one or more the mix acid liquor in hydrochloric acid, nitric acid and sulphuric acid；
(3), under conditions of stirring, in reactor, fluorine-containing acid solution is added, and hydrochloric acid and/or nitric acid, described fluoric-containing acid
Liquid is Fluohydric acid. and/or hexafluosilicic acid, opens the chiller in response system and exhaust gas absorption device, will prepare in step (2)
Material put in reactor, continuously stirred during feeding intake, the reaction temperature controlled in reactor is 70～95 DEG C, fluoric-containing acid
Fluohydric acid. or hexafluosilicic acid in liquid generate silicon tetrafluoride gas with the silicon dioxde reaction in material, and this gas part is dissolved in instead
Answer the silicon dioxide formed in the water of system in hexafluosilicic acid continuation dissolving flyash, another part silicon tetrafluoride gas and mixed acid
The sour gas and the steam that are volatilized in liquid are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 10～36 DEG C, mixed gas react in cooling reactor generate HF,
Cl2/NO2、SiO2·nH2O, wherein HF and Cl2/NO2Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generation and be available for repeating to make
Fluohydric acid., hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects in cooling reactor
SiO2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes the acidity wherein remained
Gas HF and Cl2/NO2, it is dried the most again, can be prepared by aerosil product after drying, SiO in product2Content is big
In 99.9%, its multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), reaction kettle for reaction complete after filter, obtain filtering residue and filtrate, filtrate reused after purification.
The most first by flyash activation processing at 750～950 DEG C in step (1), grind use wet grinding mill or
Person's dry method is ground.
Acid solution collection after removing is processed by step (2), reclaims valuable metal therein or preparation aluminium salt product, such as:
Aluminum sulfate, aluminium polychlorid etc..
In hot acid liquid described in step (2) and the mix acid liquor described in step (3), the mass concentration of Fluohydric acid. or volume
Concentration is 10～40%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, the mass concentration of nitric acid or volumetric concentration
Being 10～20%, the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%, and the mass concentration of sulphuric acid or volumetric concentration are
10%～40%.
Described device includes that hot-air sends into system, chemical reaction system, cooling system and waste gas absorbing system, wherein
Hot-air send into system for storing compressed air and send into after air is heated chemical reaction system and in；Described chemistry
Response system is made up of acid solution storage tank, feed bin and reactor, and acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin
Logical, it is provided with agitating device in reactor, the liner of reactor is heatproof, acidproof, high-abrasive material, upper bottom reactor
Side, is provided with an annular pipe, pipe is evenly distributed with air-vent or permeability cell, be provided with more than one in reactor
The vertical tube being connected with the pipe of annular, the top of described vertical tube sends into system by the pipe valve on the kettle cover of reactor with hot-air
System is connected；Still inwall is provided with from top to bottom or from bottom to top is close to still wall and helically wire tetrafluoro bundle of capillary tubes,
The two ends up and down of this tube bank respectively with still wall outside cold and hot medium be connected by its valve, by give tube bank in capillary tube be passed through
Cold and hot medium, provides for response system in still and is heated or cooled；
Cooling system is composed in series by one-level cooling reactor and two grades of cooling reactors；Wherein one-level cooling reactor is connected with reactor
Connecing, the kettle cover of reactor is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center with one-level cooling reactor, and one
Level cooling reactor be internally provided with chiller, the bottom of one-level cooling reactor is provided with outlet valve, on the kettle cover of one-level cooling reactor
It is provided with one be connected with two grades of cooling reactors and be deep into the pipeline of two grades of cooling reactor bottom center, two grades of described cooling reactors
Being internally provided with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；One it is provided with on the kettle cover of two grades of cooling reactors
The pipeline being connected with waste gas absorbing system, described waste gas absorbing system is inhaled by more than one negative pressure water tourie and acid mist
Receiving apparatus forms, and the top of negative pressure water tourie is provided with pipeline and is connected with the air-introduced machine in acid mist absorbing device by pipeline
Connect.
Described hot-air is sent into system and is included air compressor, air storage tank, air heater and pipeline, air pressure
Contracting machine, air storage tank and air heater are connected by pipeline, and pipeline is additionally provided with valve and instrument.
A diameter of 10～20mm's and towards different permeability cells, adjacent permeability cell it are evenly distributed with on described pipe
Between spacing be 50～150mm, and the angle stretched out between direction of adjacent permeability cell is 60～120 °, sets in reactor
Being equipped with two vertical tubes, described two vertical tubes are connected to the two ends, left and right of pipe.
The chiller of described one-level cooling reactor is made up of rotating shaft and cooling disk, and described rotating shaft is that an outer wrap has
The hollow circular-tube of politef, the top of rotating shaft is stretched out on the kettle cover by one-level cooling reactor, is provided with one from upper in rotating shaft
Cooling water pipe A under and, the top of cooling water pipe A is water inlet end and water inlet end is connected with cooling water source；Uniformly divide in rotating shaft
Being furnished with cooling disk, described cooling disk is fixed in rotating shaft with rotating shaft for the center of circle, and rotates with rotating shaft, described cooling circle
Dish 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 of the cooling water pipe B in the cooling disk of bottommost and cooling water pipe A
Bottom be connected, hollow circular-tube is led in the water side of cooling water pipe B in the cooling disk of top, arranges in cooling water pipe B
The cooling water gone out is overflowed by the top of rotating shaft；It is evenly distributed with vertical passage on described cooling disk, and neighbouring
Cooling disk on passage mutual dislocation.
The kettle cover of described one-level cooling reactor is provided with the manhole of vacuum meter and easy access, on the kettle cover of one-level cooling reactor
Being additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.
The described chiller in two grades of cooling reactors is multilamellar fin structure, the still wall of two grades of cooling reactors is provided with cold
But water inlet and coolant outlet, cooling water inlet is connected with the water inlet of orlop fin, and cooling water is by undermost wing
Sheet flows into, and described fin is Curved Continuous folded structure, and the end of the adjacent fin of two-layer up and down is connected, coolant outlet with go up most
The outlet of layer fin is connected；Being provided with compressed air blowning installation on the kettle cover of two grades of cooling reactors, compressed air is blown and is filled
Putting and be connected with compressed gas source, the kettle cover of two grades of cooling reactors is provided with vacuum meter, and its kettle cover and bottom are designed with being easy to inspection
The manhole repaiied.
Compared with prior art, technical scheme provided by the present invention has the advantage that 1, the present invention is with flyash etc.
Garbage, as raw material, is prepared into the product gas phase silicon dioxide of high added value, SiO in obtained product2Content is big
In 99.9%, its multiple spot BET method measurement the specific area is not less than 350m2/ g, has therefore reached the effect turned waste into wealth.2, this
Bright provided preparation technology belongs to a kind of brand-new technique thinking, solves institute in existing aerosil preparation technology
Exist high-temperature process, use the shortcomings such as breakneck inflammable and explosive hydrogen and oxygen.Production work provided by the present invention
Artistic skill is prepared the most at normal temperatures and pressures.3, produced by the preparation technology of the present invention, sour gas is through negative pressure water tourie
After absorption, it is possible to prepare corresponding acid solution, can be recycled after acid solution is concentrated to certain concentration, it is possible to greatly save
Cost in production and the problem of environmental protection treatment waste water.4, the process units that the present invention provides is capable of large-scale industry metaplasia
Produce, and used parts are chemical plant common tool, with low cost.
Accompanying drawing explanation
The overall structure schematic diagram of the preparation facilities that Fig. 1 provides for the present invention；
Fig. 2 is the structural representation cooling down disk in one-level cooling reactor；
Fig. 3 is the structural representation of fin in two grades of cooling reactors；
In figure: 1-acid solution storage tank, 2-feed bin, 3-reactor, 4-agitating device, 5-pipe, 6-vertical tube, 7-one-level cools down
Still, bis-grades of cooling reactors of 8-, 9-outlet valve, 10-negative pressure water tourie, 11-acid mist absorbing device, 12-air compressor, 13-is empty
Gas holding vessel, 14-air heater, 15-rotating shaft, 16-cools down disk, 17-cooling water pipe A, 18-passage, 19-fin.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the present invention is done detailed specific description by specific embodiment, but protection scope of the present invention
It is not limited to following example.
The structure of the preparation facilities provided in the present embodiment as it is shown in figure 1, described device include hot-air send into system,
Chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air sends into system for storing compressed air right
Air is sent in chemical reaction system after heating, and described hot-air is sent into system and included that air compressor 12, air store up
Depositing tank 13, air heater 14 and pipeline, air compressor 12, air storage tank 13 and air heater 14 are by pipeline phase
Connect, pipeline is additionally provided with valve and instrument.
Described chemical reaction system is made up of acid solution storage tank 1, feed bin 2 and reactor 3, acid solution storage tank 1 and the bottom of feed bin 2
Being connected with reactor 3 by pipeline, be provided with agitating device 4 in reactor 3, the liner of reactor is heatproof, acidproof, wear-resisting
Material, specifically selects carborundum, fluorine material, graphite material etc..Above bottom reactor 3, about 200mm place, is provided with one
The pipe 5 of annular, a diameter of the 100 of described pipe～200mm, described pipe 5 is evenly distributed with a diameter of 10～20mm
And towards different permeability cells, the adjacent spacing between permeability cell is 50～150mm, and the side of stretching out of adjacent permeability cell
Angle between to is 60～120 °.Two vertical tubes 6 being connected with the pipe of annular, two vertical tubes 6 it are provided with in reactor
Being connected to the two ends, left and right of pipe 5, the top of described vertical tube 6 is sent into hot-air by the pipe valve on the kettle cover of reactor
System is connected.Still wall in reactor has spiral to link up with, for heating or the politef of cooling in supporting still
Bundle of capillary tubes.
Cooling system is composed in series by one-level cooling reactor 7 and two grades of cooling reactors 8；Wherein one-level cooling reactor 7 and reactor 3 phase
Connecting, the kettle cover of reactor 3 is provided with a pipe being connected and be deep into one-level cooling reactor bottom center with one-level cooling reactor 7
Road, one-level cooling reactor 7 be internally provided with chiller, the chiller of described one-level cooling reactor is by rotating shaft 15 and cooling disk
16 compositions, described rotating shaft 15 is the hollow circular-tube that an outer wrap has politef, and the top of rotating shaft is by one-level cooling reactor
Kettle cover on stretch out, be provided with a top-down cooling water pipe A17 in rotating 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 it is evenly distributed with in rotating shaft 15.Cooling disk structure as in figure 2 it is shown,
Described cooling disk 16 is fixed in rotating shaft with rotating shaft 15 for the center of circle, and rotates with rotating shaft, and described cooling disk is hollow
Structure, the inside of all cooling disks is provided with in the cooling water pipe B of distribution in spiral shape, and neighbouring cooling disk
Cooling water pipe B join end to end, the water inlet end of cooling water pipe B in the cooling disk of bottommost and the bottom phase of cooling water pipe A
Connecting, hollow circular-tube is led in the water side of the cooling water pipe B in the cooling disk of top, the cooling discharged in cooling water pipe B
Water is overflowed by the top of rotating shaft.It is evenly distributed with vertical passage 18, and neighbouring cooling on described cooling disk
Passage mutual dislocation on disk, to ensure the cooling effect of its gas.A diameter of the 10 of described passage～20mm, adjacent
Passage between centre-to-centre spacing be 20mm～30mm.
The kettle cover of described one-level cooling reactor is provided with the manhole of vacuum meter and easy access, on the kettle cover of one-level cooling reactor
Being additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.The kettle cover of one-level cooling reactor 7
On be provided with a pipeline being connected and be deep into two grades of cooling reactor 8 bottom center with two grades of cooling reactors 8.The end of one-level cooling reactor
Portion is provided with outlet valve 9.
Two grades of described cooling reactors 8 be internally provided with chiller, the described chiller in two grades of cooling reactors is
Multilamellar fin structure, the still wall of two grades of cooling reactors 8 is provided with cooling water inlet and coolant outlet, cooling water inlet with under
Layer fin water inlet be connected, cooling water flowed into by undermost fin, described fin 19 in Curved Continuous folded structure, its structure
As shown in Figure 3.The end of the adjacent fin of two-layer up and down is connected, and coolant outlet is connected with the outlet of the superiors' fin
Logical, cooling water enters from orlop fin, flows out to one layer of fin topmost.It is provided with compression on the kettle cover of two grades of cooling reactors
Air puff device, compressed air blowning installation is connected with compressed gas source, purges by compressed air during discharging.Two grades of coolings
The kettle cover of still is provided with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.The bottom of two grades of cooling reactors is arranged
There is outlet valve 9；A pipeline being connected with waste gas absorbing system it is provided with on the kettle cover of two grades of cooling reactors 8.
Described waste gas absorbing system is made up of two negative pressure water touries 10 and acid mist absorbing device 11, two negative pressure water
Tourie is in series or is connected in parallel.The top of negative pressure water tourie is provided with pipeline and by pipeline and acid mist absorbing device
Air-introduced machine be connected.Acid mist after two grades of water touries absorb droplet with liquid caustic soda solution in acid mist absorbing device occurs
It is discharged into again in air after neutralizing reaction, makes when giving workshop circulation after the concentration that the acid solution of negative pressure water tourie reaches certain
With.
As a example by the flyash that certain power plant is produced, the technique that processes in detail of the present invention is elaborated below.Concrete
Process technique is as follows:
(1), first by flyash activation processing at 750～950 DEG C, flyash is ground to particle diameter the most again less than 200
Mesh sieve, grinds and uses wet grinding mill or dry method mill, by drying materials after then grinding according to wet grinding mill.Use magnetic separation the most again
Machine iron removal by magnetic separation, then analyzes SiO therein2、TiO2、Al2O3、Fe2O3、MgO、CaO、K2O、Na2The content of O.
(2), will grind after material use hot acid liquid process, heating under conditions of the most molten except in material
Al2O3、Fe2O3、TiO2、MgO、CaO、K2O、Na2After O standby, removing acid solution and wash, be dehydrated after standby, described acid solution is
One or more mix acid liquor in hydrochloric acid, nitric acid and sulphuric acid, in the present embodiment select mass concentration be 10%～
The hydrochloric acid of 30%.The most individually process after acid solution after removing is collected, be used for preparing aluminium polychlorid product.
(3), under conditions of stirring, in reactor, fluorine-containing acid solution is added, and hydrochloric acid and/or nitric acid, described fluoric-containing acid
Liquid is Fluohydric acid. and/or hexafluosilicic acid, both can first add Fluohydric acid. and/or hexafluosilicic acid, then add hydrochloric acid and/or nitre in the present invention
Acid, it is also possible to add together after above acid solution is mixed.The chiller being then turned in response system and exhaust gas absorption device,
The material prepared in step (2) is put in reactor, continuously stirred during feeding intake.
If the fluorine-containing acid solution added is Fluohydric acid., owing to it and silicon dioxde reaction process are exothermic process, then
Cooling water valve outside reaction response still need to be opened and maintain reaction temperature 70～95 DEG C.If the mix acid liquor put into does not contains
Fluohydric acid. and containing hexafluosilicic acid, then need the steam opening reacting kettle jacketing slowly to heat to reactor.Hydrogen fluorine in fluorine-containing acid solution
Acid or hexafluosilicic acid generate silicon tetrafluoride gas with the silicon dioxde reaction in material, and this gas part is dissolved in the water of reaction system
Middle formation hexafluosilicic acid continues to dissolve the silicon dioxide in the flyash after purifying, another part silicon tetrafluoride gas and mix acid liquor
Middle volatilized sour gas and steam are brought in cooling reactor by negative pressure together.Fluohydric acid. employed in the present embodiment
Mass concentration or volumetric concentration are 10～40%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, the quality of nitric acid
Concentration or volumetric concentration are 10～20%, and the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%, the mass concentration of sulphuric acid
Or volumetric concentration is 10%～40%.
(4), the chilling temperature controlled in cooling reactor be 10～36 DEG C, mixed gas react in cooling reactor generate HF,
Cl2/NO2、SiO2·nH2O, chemical equation is as follows:
SiF4+4HNO3+nH2O=4HF ↑+4NO2↑+SiO2·nH2O
SiF4+4HCl+nH2O=4HF ↑+Cl2↑+SiO2·nH2O
Wherein HF and Cl2/NO2Taken out of from one-level cooling reactor and two grades of cooling reactors by negative pressure, enter waste gas absorbing system also
Being only absorbed by the water generation and be available for reusable Fluohydric acid., hydrochloric acid/nitric acid, this Fluohydric acid., hydrochloric acid/nitric acid are concentrated to certain concentration
After can be recycled；The cost in producing and the problem of environmental protection treatment waste water are the most greatly saved.
And SiO2·nH2O slowly condenses on absorption cooling disk in one-level cooling reactor, from starting on cooling disk
Cohesion, then knot, in glittering and translucent spherical particle, flocks together as fish roe the most naturally, the most attractive in appearance, when one-level is cold
But, when the cooling disk of still gathers a certain amount, opening of rotary shaft device, rotating shaft drives cooling disc rotary, at the work of centrifugal force
Under with, material is thrown to still wall, then blows to the bottom of one-level cooling reactor by compressed air, and the outlet valve through bottom is sent to be dried
Operation；After having processed the material of one-level cooling reactor, two grades of cooling reactors the most directly open compressed air valve, directly the thing condensed
After expecting to blow to bottom, the outlet valve through bottom is sent to drying process.
(5), owing to material contains moisture, it is acidity, and Fluohydric acid., Silicon fluoride. and nitric acid or the volatilization of HCl gas
Property is extremely strong, the most before it is dried, first by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein
Sour gas HF and Cl of residual2/NO2, it is dried the most again, can be prepared by aerosil product after drying, in product
SiO2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/g。
(6), owing to the mix acid liquor in above-mentioned reaction is excessive, the silicon dioxde reaction in flyash is very complete, instead
Should remain the material in still afterwards and be mainly the acid solution of tiny carbon granule and surplus, filtered while hot, the acid solution after filtration is through pure
After change, repeat use；The soot particulate matter filtered out, after tap water rinse, then is washed till neutrality, after dehydration and purification, spends
Ionized water washs 3 times, dehydration, dried, and packaging is i.e. highly purified charcoal particulate matter.
Claims (10)
1. a flyash integrated treatment utilize method, it is characterised in that comprise the following steps: (1), by flyash grind
To particle diameter less than 200 mesh sieves, then use magnetic separator iron removal by magnetic separation, then analyze the content of wherein each composition；
(2), will grind after material use hot acid liquid to process, molten except metal-oxide therein, removing acid solution is also washed, is dehydrated
The most standby, described acid solution is one or more the mix acid liquor in hydrochloric acid, nitric acid and sulphuric acid；
(3), under conditions of stirring, in reactor, fluorine-containing acid solution is added, and hydrochloric acid and/or nitric acid, described fluorine-containing acid solution is
Fluohydric acid. and/or hexafluosilicic acid, open the chiller in response system and exhaust gas absorption device, the thing that will prepare in step (2)
Material puts in reactor, continuously stirred during feeding intake, and the reaction temperature controlled in reactor is 70～95 DEG C, in fluorine-containing acid solution
Fluohydric acid. or hexafluosilicic acid and material in silicon dioxde reaction generate silicon tetrafluoride gas, this gas part is dissolved in reactant
The water of system is formed hexafluosilicic acid continue to dissolve in the silicon dioxide in flyash, another part silicon tetrafluoride gas and mix acid liquor
The sour gas and the steam that are volatilized are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 10～36 DEG C, mixed gas react in cooling reactor and is generated HF, Cl2/NO2、
SiO2·nH2O, wherein HF and Cl2/NO2Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generation and be available for reusable hydrogen
Fluoric acid, hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects the SiO in cooling reactor2·
nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes the sour gas wherein remained
HF and Cl2/NO2, it is dried the most again, can be prepared by gas-phase silica product after drying, SiO in product2Content is more than
99.9%, its multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), reaction kettle for reaction complete after filter, obtain filtering residue and filtrate, filtrate reused after purification.
The method that the integrated treatment of flyash the most according to claim 1 utilizes, it is characterised in that: step is being ground in (1)
First by flyash activation processing at 750～950 DEG C before mill, grind and use wet grinding mill or dry method mill.
The method that the integrated treatment of flyash the most according to claim 1 utilizes, it is characterised in that: will be de-in step (2)
Acid solution collection after removing processes, and reclaims valuable metal therein or preparation aluminium salt product.
The method that the integrated treatment of flyash the most according to claim 1 utilizes, it is characterised in that: described in step (2)
In mix acid liquor described in hot acid liquid and step (3), the mass concentration of Fluohydric acid. or volumetric concentration are 10～40%, hexafluosilicic acid
Mass concentration or volumetric concentration be 10～30%, the mass concentration of nitric acid or volumetric concentration are 10～20%, the quality of hydrochloric acid
Concentration or volumetric concentration are 10%～30%, and the mass concentration of sulphuric acid or volumetric concentration are 10%～40%.
5. the device in method of comprehensive utilization described in claim 1, it is characterised in that: described device includes hot-air
Feeding system, chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air feeding system is used for storing compression
Air and send into after air is heated chemical reaction system and in；Described chemical reaction system by acid solution storage tank, feed bin and
Reactor forms, and acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin, is provided with agitating device in reactor,
The liner of reactor is heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular pipe, on pipe
It is evenly distributed with air-vent or permeability cell, in reactor, is provided with the vertical tube that the pipe with annular of more than is connected, institute
The top stating vertical tube is connected with hot-air feeding system by the pipe valve on the kettle cover of reactor；Still inwall from top to bottom or from
Lower and on be provided with and be close to still wall and helically wire tetrafluoro bundle of capillary tubes, outside the two ends up and down of this tube bank are respectively with still wall
Cold and hot medium connected by its valve, by give tube bank in capillary tube be passed through cold and hot medium, provide for response system in still
It is heated or cooled；
Cooling system is composed in series by one-level cooling reactor and two grades of cooling reactors；Wherein one-level cooling reactor is connected with reactor, instead
The kettle cover answering still is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center with one-level cooling reactor, and one-level cools down
Still be internally provided with chiller, the bottom of one-level cooling reactor is provided with outlet valve, and the kettle cover of one-level cooling reactor is provided with
One is connected with two grades of cooling reactors and is deep into the pipeline of two grades of cooling reactor bottom center, and the inside of two grades of described cooling reactors sets
Being equipped with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；One and waste gas it is provided with on the kettle cover of two grades of cooling reactors
The pipeline that absorption system is connected, described waste gas absorbing system is by more than one negative pressure water tourie and acid mist absorbing device
Composition, the top of negative pressure water tourie is provided with pipeline and is connected with the air-introduced machine in acid mist absorbing device by pipeline.
Device the most according to claim 5, it is characterised in that: described hot-air send into system include air compressor,
Air storage tank, air heater and pipeline, air compressor, air storage tank and air heater are connected by pipeline
Connect, pipeline is additionally provided with valve and instrument.
Device the most according to claim 5, it is characterised in that: it is evenly distributed with a diameter of 10～20mm on described pipe
And towards different permeability cells, the adjacent spacing between permeability cell is 50～150mm, and the side of stretching out of adjacent permeability cell
Angle between to is 60～120 °, is provided with two vertical tubes in reactor, and described two vertical tubes are connected to a left side for pipe
Right two ends.
Device the most according to claim 5, it is characterised in that: the chiller of described one-level cooling reactor is by rotating shaft and cooling disk
Composition, described rotating shaft is the hollow circular-tube that an outer wrap has politef, and the top of rotating shaft is by the still of one-level cooling reactor
Covering and stretch out, be provided with a top-down cooling water pipe A in rotating shaft, the top of cooling water pipe A is water inlet end and water inlet end
It is connected with cooling water source；Being evenly distributed with cooling disk in rotating shaft, described cooling disk is fixed on rotating shaft for the center of circle
In rotating shaft, and rotating with rotating shaft, described cooling disk is hollow structure, and the inside of all cooling disks is provided with in spiral shape
Cooling water pipe B in the cooling water pipe B of distribution, and neighbouring cooling disk joins end to end, in the cooling disk of bottommost
The water inlet end of cooling water pipe B be connected with the bottom of cooling water pipe A, the going out of cooling water pipe B in the cooling disk of top
Water end (W.E.) leads to hollow circular-tube, and the cooling water discharged in cooling water pipe B is overflowed by the top of rotating shaft；On described cooling disk uniformly
Passage mutual dislocation vertical passage, and neighbouring cooling disk on is distributed.
Device the most according to claim 8, it is characterised in that: the kettle cover of described one-level cooling reactor be provided with vacuum meter and
The manhole of easy access, the kettle cover of one-level cooling reactor is additionally provided with compressed air blowning installation, compressed air blowning installation with
Compressed gas source is connected.
Device the most according to claim 5, it is characterised in that: the described chiller in two grades of cooling reactors is multilamellar
Fin structure, the still wall of two grades of cooling reactors is provided with cooling water inlet and coolant outlet, cooling water inlet and orlop wing
The water inlet of sheet is connected, and cooling water is flowed into by undermost fin, and described fin is Curved Continuous folded structure, and adjacent up and down two
The end of layer fin is connected, and coolant outlet is connected with the outlet of the superiors' fin；Set on the kettle cover of two grades of cooling reactors
Being equipped with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source, and the kettle cover of two grades of cooling reactors sets
There is vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317353A (en) * | 2001-02-28 | 2001-10-17 | 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 |
| CN101214961A (en) * | 2007-12-30 | 2008-07-09 | 薛彦辉 | Method for preparing white carbon black, coal powder and aluminum hydroxide from fly ash |
| CN101596438A (en) * | 2009-07-10 | 2009-12-09 | 浙江大学 | Be suitable for the adjustable twin shaft reactor that variable physical property medium stirs |
| 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 |
| 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 |
| 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 |
| CN102701221A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for preparing nano white carbon black from coal gangue |
| CN102921356A (en) * | 2012-10-22 | 2013-02-13 | 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 |
| CN103420383A (en) * | 2013-07-29 | 2013-12-04 | 中国化学赛鼎宁波工程有限公司 | Method for preparing fumed silica and anhydrous hydrofluoric acid by utilizing phosphatic fertilizer by-product fluosilicate as raw material |
| CN103663474A (en) * | 2013-12-20 | 2014-03-26 | 瓮福（集团）有限责任公司 | Method for preparing white carbon black from silicon slags containing fluorine |
| CN104803391A (en) * | 2015-02-15 | 2015-07-29 | 贵州天合国润高新材料科技有限公司 | Method used for preparing flake-like silicon dioxide powder |
| CN104828829A (en) * | 2015-05-11 | 2015-08-12 | 蚌埠玻璃工业设计研究院 | Heat-conducting closed continuous scrubbing-leaching equipment |
| CN105110344A (en) * | 2015-08-19 | 2015-12-02 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
| CN105314599A (en) * | 2015-11-17 | 2016-02-10 | 龚兴荣 | Method for producing anhydrous hydrogen fluoride and white carbon black through fluosilicic acid |
| CN105368501A (en) * | 2014-09-01 | 2016-03-02 | 大唐国际化工技术研究院有限公司 | Protecting mechanism of technological burner applicable to entrained-flow bed coal gasifier |
| CN105797669A (en) * | 2016-05-20 | 2016-07-27 | 广西锦华新材料科技有限公司 | Comprehensive treatment device for preparing chlorinated polyethylene |
-
2016
- 2016-08-23 CN CN201610703692.5A patent/CN106315597B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317353A (en) * | 2001-02-28 | 2001-10-17 | 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 |
| CN101214961A (en) * | 2007-12-30 | 2008-07-09 | 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 |
| CN101596438A (en) * | 2009-07-10 | 2009-12-09 | 浙江大学 | Be suitable for the adjustable twin shaft reactor that variable physical property medium stirs |
| 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 |
| 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 |
| CN102701221A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for preparing nano white carbon black from coal gangue |
| CN102921356A (en) * | 2012-10-22 | 2013-02-13 | 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 |
| CN103420383A (en) * | 2013-07-29 | 2013-12-04 | 中国化学赛鼎宁波工程有限公司 | Method for preparing fumed silica and anhydrous hydrofluoric acid by utilizing phosphatic fertilizer by-product fluosilicate as raw material |
| CN103663474A (en) * | 2013-12-20 | 2014-03-26 | 瓮福（集团）有限责任公司 | Method for preparing white carbon black from silicon slags containing fluorine |
| CN105368501A (en) * | 2014-09-01 | 2016-03-02 | 大唐国际化工技术研究院有限公司 | Protecting mechanism of technological burner applicable to entrained-flow bed coal gasifier |
| CN104803391A (en) * | 2015-02-15 | 2015-07-29 | 贵州天合国润高新材料科技有限公司 | Method used for preparing flake-like silicon dioxide powder |
| CN104828829A (en) * | 2015-05-11 | 2015-08-12 | 蚌埠玻璃工业设计研究院 | Heat-conducting closed continuous scrubbing-leaching equipment |
| CN105110344A (en) * | 2015-08-19 | 2015-12-02 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
| CN105314599A (en) * | 2015-11-17 | 2016-02-10 | 龚兴荣 | Method for producing anhydrous hydrogen fluoride and white carbon black through fluosilicic acid |
| CN105797669A (en) * | 2016-05-20 | 2016-07-27 | 广西锦华新材料科技有限公司 | Comprehensive treatment device for preparing chlorinated polyethylene |
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