CN105967190A - Process and device for preparing gas-phase white carbon black by taking quartziferous fluorite tailings as raw materials - Google Patents
Process and device for preparing gas-phase white carbon black by taking quartziferous fluorite tailings as raw materials Download PDFInfo
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- CN105967190A CN105967190A CN201610534931.9A CN201610534931A CN105967190A CN 105967190 A CN105967190 A CN 105967190A CN 201610534931 A CN201610534931 A CN 201610534931A CN 105967190 A CN105967190 A CN 105967190A
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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
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/183—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane
- C01B33/184—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane by hydrolysis of tetrafluoride
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- C—CHEMISTRY; METALLURGY
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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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
- C01F7/50—Fluorides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention provides a process for preparing gas-phase white carbon black at a low temperature by taking quartziferous fluorite tailings as raw materials. In the process, wastes including the quartziferous fluorite tailings and the like are used as the raw materials and are reacted with fluorine-containing acid liquid, hydrochloric acid and nitric acid to prepare the product gas-phase white carbon black with a high additional value and high-valence metal and fluorite powder are recycled; in the prepared product, the content of SiO2 is more than 99.9 percent and the specific surface area measured by a multi-point BET method is: 350m<2>/g to 500m<2>/g, so that the effect of changing wastes into valuable things is realized; after acidic gas generated in the preparation process is absorbed by a negative-pressure water absorption tank, corresponding acid liquid can be prepared; when the acid liquid is concentrated to a certain concentration, the acid liquid can be circularly utilized. Meanwhile, the invention further provides a production device used for the process; all parts of the production device are common devices in chemical plants and the cost is low, so that large-scale industrial production can be realized.
Description
Technical field
The present invention relates to a kind of process and device utilizing quartziferous fluorite mine tailing to prepare gas-phase silica, belong to chemical industry
Purify and environmental technology field.
Background technology
Fluorite ore is one of a kind of important nonmetallic minerals strategic resource of China, and it is mainly used in being fluorinated work, fluorine material
Industry.Could be used for after having to pass through purification by mineral after fluorite ore is mined being fluorinated work and fluorine materials industry, at mineral
Often producing substantial amounts of mine tailing in ore dressing and purification process, mine tailing is stacked need to take substantial amounts of soil, and it destroys ecology
Environment, becomes serious Hidden hazrads.Therefore, if quartziferous quartziferous fluorite resource of tailings can be utilized scientific development,
It is possible not only to save substantial amounts of land resource, beautifies our production and working environment, and it is hidden to eliminate serious disaster
Suffering from, it is also possible to improve the economic benefit of enterprise, the most also the sustainable development for fluorite deep processing industry has been explored new
Approach.
Vapor phase method is prepared the raw material of white carbon and is generally Silicon chloride., oxygen (or air) and hydrogen, under high temperature reaction and
Become.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)；
The fume colloidal silica granule now generated is superfine, forms aerosol with gas, is difficult to trapping, therefore makes it first at collector
In be gathered into larger particles, then through cyclone collection, be re-fed into deacidification furnace, with nitrogenous air blowing gas phase dioxy
SiClx to pH value is 4～6 to be finished product.China produces the enterprise of gas-phase silica at present and mostly uses this method, and this method is also
It it is the production method of the most general gas-phase silica.Ye You enterprise of China uses methyl trichlorosilane to produce gas phase Linesless charcoal
Black, and have successfully completed industrialized production.The production technology of fume colloidal silica now does not only exist high-temperature process,
But also use breakneck and inflammable and explosive hydrogen and oxygen, in its production process, the operating environment of workman compares
Arduous；Safety coefficient is required the highest.Consult related data and Chinese patent literature, do not find to utilize other raw materials raw
Produce the relevant report of gas-phase silica.
Summary of the invention
The invention provides a kind of with quartziferous fluorite mine tailing as raw material, prepare manufacturing technique method and the dress of gas-phase silica
Put；It successfully avoids and uses hydrogen and the technique mistake of oxygen and pyrohydrolysis now in gas-phase silica preparation process
Journey, also solves the problem that current quartziferous fluorite mine tailing can not efficiently utilize, and the present invention additionally provides at room temperature simultaneously
Novel technique and the process units of gas-phase silica product can be produced under normal pressure.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of technique preparing gas-phase silica for raw material with quartziferous fluorite mine tailing, it is characterised in that comprise the following steps:
(1), by fluorine-containing acid solution, mix with one or both in nitric acid, hydrochloric acid, prepare mix acid liquor standby；By stone
English matter fluorite mine tailing is ground to the fineness of below 200 mesh, with magnetic separator magnetic separation more than 10000 Gausses in grinding process
Except ferrum, prepare powder；
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
Device, puts into powder in reactor；
(3), the reaction temperature controlled in reactor be 70～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and quartz
Silicon dioxde reaction in matter fluorite mine tailing generates silicon tetrafluoride gas, is volatilized in this silicon tetrafluoride gas and mix acid liquor
Sour gas and steam brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 0～36 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 can
For reusable Fluohydric acid., hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects
SiO in cooling reactor2·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 gas-phase silica product after drying, SiO in product2
Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), in a kettle., mix acid liquor is oxidized to sulphuric acid the sulfur component in powder, after reaction kettle for reaction completes,
Filtered while hot, obtains filtering residue and filtrate, washes filtering residue with water neutrality, sells or be used as after the filter residue and drying washed
Cement adds material；Or filtering residue is carried out flotation again, i.e. can get highly purified Fluorspar Powder and borontrifluoride aluminium powder.
The mass concentration of described Fluohydric acid. or volumetric concentration are 1～20%, and the mass concentration of hexafluosilicic acid or volumetric concentration are
10～30%, the mass concentration of nitric acid or volumetric concentration are 2～30%, the mass concentration of hydrochloric acid or volumetric concentration be 10%～
30%.
The powder acid solution washing prepared in step (1) is removed calcium, after, then after removing acid solution washing material,
Last processed.
Filtrate after filtering in step (6) first carries out evaporation and concentration, after the sour gas use water of volatilization absorbs, forms acid
Liquid, returns again to workshop and uses；After filtrate being finally evaporated, metallic salt mixture can be obtained, metallic salt is mixed
Thing is tested, and carries out according to test result separating, purifying again, i.e. can get corresponding metal.
Present invention also offers the device in above-mentioned technique, described device includes that hot-air sends into system, chemical reaction
System, cooling system and waste gas absorbing system, wherein air for storing compressed air and is entered by hot-air feeding system
Send in chemical reaction system after row heating；Described chemical reaction system is made up of acid solution storage tank, feed bin and reactor, acid
Liquid storage tank is connected with reactor by pipeline with the bottom of feed bin, is provided with agitating device in reactor, reactor interior
Lining for heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular pipe, on pipe uniformly
Air-vent or permeability cell are distributed, in reactor, are provided with the vertical tube that the pipe with annular of more than is connected, described
The top of vertical tube is sent into system by the pipe valve on the kettle cover of reactor with hot-air and is connected；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, the two ends up and down of this tube bank respectively with still wall
Outer cold and hot medium is connected by its valve, by being passed through cold and hot medium, for response system in still to the capillary tube in restraining
Offer 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,
The kettle cover of reactor is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center, one-level with one-level cooling reactor
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 the pipeline for two grades of cooling reactor bottom center that is connected with two grades of cooling reactors and is deep into, two grades of described cooling reactors
Be internally provided with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；It is provided with on the kettle cover of two grades of cooling reactors
A piece pipeline being connected with waste gas absorbing system, described waste gas absorbing system by more than one negative pressure water tourie and
Acid mist absorbing device forms, and the top of negative pressure water tourie is provided with pipeline and by pipeline and drawing in acid mist absorbing device
Blower fan is connected.
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 °, reaction
Being provided with two vertical tubes in still, 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 poly-
The hollow circular-tube of tetrafluoroethene, 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；In rotating shaft all
The even cooling disk that is distributed, described cooling disk is fixed in rotating shaft with rotating shaft for the center of circle, and rotates with rotating shaft, institute
Stating cooling 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
The neighbouring cooling water pipe B in cooling disk joins end to end, the cooling water pipe B's in the cooling disk of bottommost
Water inlet end is connected with the bottom of cooling water pipe A, and the water side of the cooling water pipe B in the cooling disk of top is led to
Hollow circular-tube, the cooling water discharged in cooling water pipe B is overflowed by the top of rotating shaft；It is uniformly distributed on described cooling disk
There is the passage mutual dislocation on vertical passage, and neighbouring cooling disk.
A diameter of the 10 of described passage～20mm, the adjacent centre-to-centre spacing between passage is 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 also
Being 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, and the still wall of two grades of cooling reactors is provided with cooling
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 flow into, 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
The outlet of the superiors' fin is connected；Compressed air blowning installation, compressed air it is provided with on the kettle cover of two grades of cooling reactors
Blowning installation is connected with compressed gas source, and the kettle cover of two grades of cooling reactors is provided with vacuum meter, and its kettle cover and bottom all set
There is the manhole of easy access.
Described negative pressure water tourie is provided with two, and two negative pressure water touries are in series or are connected in parallel.
Compared with prior art, technical scheme provided by the present invention has the advantage that 1, the present invention is with quartziferous firefly
Stone mine tailing the like waste, as raw material, is prepared into the product gas phase white carbon of high added value, in obtained product
SiO2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/ g, therefore reached become give up into
Precious effect.2, preparation technology provided by the present invention belongs to a kind of brand-new technique thinking, solves existing gas phase
High-temperature process in the presence of white carbon preparation technology, use the shortcomings such as breakneck inflammable and explosive hydrogen and oxygen.
Production technology provided by the present invention can be prepared at normal temperatures and pressures.3, the preparation technology of the present invention is produced
Sour gas after negative pressure water tourie absorbs, it is possible to prepare corresponding acid solution, after acid solution is concentrated to certain concentration
Can be recycled, it is possible to greatly saved the cost in producing and the problem of environmental protection treatment waste water.4, the present invention provides
Process units be capable of large-scale industrial production, and used parts are chemical plant common tool, cost
Cheap.5, the present invention can reclaim for the high-valency metal in quartziferous fluorite mine tailing and Fluorspar Powder, has the biggest
Economic benefit.
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-air storage tank, 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 is also
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 also
Sending into after heating air in chemical reaction system, described hot-air is sent into system and is included air compressor 12, sky
Gas holding vessel 13, air heater 14 and pipeline, air compressor 12, air storage tank 13 and air heater
14 are connected by pipeline, and 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 feed bin 2
Bottom is connected with reactor 3 by pipeline, is provided with agitating device 4 in reactor 3, the liner of reactor be heatproof,
Acidproof, high-abrasive material, specifically selects carborundum, fluorine material, graphite material etc..200mm above bottom reactor 3
At Zuo You, it is provided with an annular pipe 5, a diameter of the 100 of described pipe～200mm, on described pipe 5 all
Even be distributed a diameter of 10～20mm's and towards different permeability cells, the adjacent spacing between permeability cell be 50～
150mm, and the angle stretched out between direction of adjacent permeability cell is 60～120 °.Be provided with in reactor two with
The vertical tube 6 that the pipe of annular is connected, two vertical tubes 6 are connected to the two ends, left and right of pipe 5, described vertical tube 6
Top is sent into system by the pipe valve on the kettle cover of reactor with hot-air and is connected.Still wall in reactor has spiral to hang
Hook, for heating or the polytetrafluoroethylene capillary bundle of cooling in supporting still.
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
Being connected, the kettle cover of reactor 3 is provided with one and is connected with one-level cooling reactor 7 and is deep into one-level cooling reactor bottom center
Pipeline, one-level cooling reactor 7 be internally provided with chiller, the chiller of described one-level cooling reactor is by rotating shaft 15
Forming with cooling disk 16, described rotating shaft 15 is the hollow circular-tube that an outer wrap has politef, the top of rotating shaft
End stretches out on the kettle cover by one-level cooling reactor, is provided with a top-down cooling water pipe A17, cooling water pipe in rotating shaft
The top of A is 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.Cold
But the structure of disk is 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 with
Rotating shaft rotates, and described cooling disk is hollow structure, and the inside of all cooling disks is provided with the cold of distribution in spiral shape
But the cooling water pipe B in water pipe B, and neighbouring cooling disk joins end to end, cold in the cooling disk of bottommost
But the water inlet end of water pipe B is connected with the bottom of cooling water pipe A, the cooling water pipe B's in the cooling disk of top
Lead to hollow circular-tube in water side, and the cooling water discharged in cooling water pipe B is overflowed by the top of rotating shaft.Described cooling disk
On be evenly distributed with vertical passage 18, and the passage mutual dislocation on neighbouring cooling disk, to ensure it
The cooling effect of gas.A diameter of the 10 of described passage～20mm, the adjacent centre-to-centre spacing between passage is
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 also
Being provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.The still of one-level cooling reactor 7
Cover and be provided with a pipeline being connected with two grades of cooling reactors 8 and be deep into two grades of cooling reactor 8 bottom center.One-level cools down
The bottom of still 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 many
Layer 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
The water inlet of lower floor's fin is connected, cooling water flowed into by undermost fin, described fin 19 in Curved Continuous folded structure,
Its structure is as shown in Figure 3.The end of the adjacent fin of two-layer up and down is connected, and coolant outlet goes out with the superiors' fin
The mouth of a river is connected, and cooling water enters from orlop fin, flows out to one layer of fin topmost.The kettle cover of two grades of cooling reactors
On be provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source, during discharging with compression sky
Air-blowing is swept.The kettle cover of two grades of cooling reactors is provided with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.Two
The bottom of level cooling reactor is provided with outlet valve 9；Be provided with on the kettle cover of two grades of cooling reactors 8 one with waste gas absorbing system phase
The pipeline connected.
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
In air-introduced machine be connected.Acid mist after two grades of water touries absorb in acid mist absorbing device with the droplet of liquid caustic soda solution
It is discharged into again in air after occurring to neutralize reaction, follows when giving workshop after the concentration that the acid solution of negative pressure water tourie reaches certain
Ring uses.
As a example by the fluorite ore mine tailing of Hunan, the detailed preparation technology of the present invention is elaborated below, through analyzing, should
In quartziferous fluorite mine tailing, each constituent content is as follows: CaF2: 16.24%, SiO2: 74.1%, Al2O3: 4.80%, Fe2O3:
0.98%, CaO:10.35%, MgO:0.14%, K2O:0.95%, NaO:0.45%.Concrete production stage is such as
Under:
(1), by one or both in Fluohydric acid., hexafluosilicic acid, mix with one or both in nitric acid, hydrochloric acid,
Preparing mix acid liquor, Fluohydric acid., hexafluosilicic acid, nitric acid or hydrochloric acid are technical grade；Or use industrial by-product.
As preferably, the mass concentration of described Fluohydric acid. or volumetric concentration are 1～20%, the mass concentration of hexafluosilicic acid or volume
Concentration is 10～30%, and the mass concentration of nitric acid or volumetric concentration are 2～30%, the mass concentration of hydrochloric acid or volumetric concentration
It is 10%～30%.
Quartziferous fluorite mine tailing is worn into 200 mesh, with magnetic separator iron removal by magnetic separation more than 10000 Gausses in grinding process,
After ferrum；With hydrochloric acid acid solution deliming,；After removing acid solution, washing material, then it is dehydrated standby.
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
Device, slowly puts into powder in reactor.
(3) if containing Fluohydric acid. in the mix acid liquor put into, owing to it and silicon dioxde reaction process are heat releases
Process, then the cooling water valve needing to open outside reaction response still maintains reaction temperature 70～85 DEG C.If the mixed acid put into
Liquid does not contains Fluohydric acid. and contains hexafluosilicic acid, then need to open the spiral shell installed on the steam valve of reacting kettle jacketing and still inwall
Thermal source valve on the still outer wall of rotation tetrafluoro bundle of capillary tubes slowly heats to reactor.Fluohydric acid. in mix acid liquor or fluorine silicon
Acid generates silicon tetrafluoride gas with the silicon dioxde reaction in quartziferous fluorite mine tailing, and this gas part is dissolved in reaction system
Water in form hexafluosilicic acid and continue to dissolve the silicon dioxide in quartziferous fluorite mine tailing, the Silicon fluoride. gas that another part overflows
Brought in cooling reactor by negative pressure together with the nitric acid/HCl gas of body and volatilization and steam.
(4), the chilling temperature controlled in cooling reactor be 0～36 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/NO2Overflow from one-level cooling reactor and two grades of cooling reactors, enter waste gas absorbing system and by water
Absorbing 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, solidifying from starting on cooling disk
Poly-, then knot, in glittering and translucent spherical particle, flocks together as fish roe the most naturally, the most attractive in appearance, work as one-level
When the cooling disk of cooling reactor gathers a certain amount, opening of rotary shaft device, rotating shaft drives cooling disc rotary, centrifugal
Under the effect of power, material is thrown to still wall, then blows to the bottom of one-level cooling reactor by compressed air, through the outlet valve of bottom
It is sent to drying process；After having processed the material of one-level cooling reactor, two grades of cooling reactors the most directly open compressed air valve,
After directly the material condensed being blown to bottom, the outlet valve through bottom is sent to drying process；
(5), owing to material contains moisture, it is acidity, and the waving of Fluohydric acid., Silicon fluoride. and nitric acid or HCl gas
The property sent out is extremely strong, the most before it is dried, first by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes
Remove sour gas HF and Cl wherein remained2/NO2, it is dried the most again, can be prepared by gas-phase silica after drying
Product, SiO in product2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/g。
(6), during above-mentioned acid liquid reaction in two kinds of situation: 1, when the sulfur content in system material is low, nitric acid
It can be oxidized to sulphuric acid, then, after having reacted, rapid filtered while hot, filtering residue carries out flotation again, i.e. can get high-purity
The Fluorspar Powder of degree and borontrifluoride aluminium powder；2, when sulfur content height in system material, nitric acid can be oxidized to sulphuric acid it,
Now adding moderate amount of sulfuric acid, after having reacted, rapid filtered while hot, filtering residue is washed with water washs neutrality, wash water conduct
Absorb and evaporation process absorbs sour gas use, be sold to cement plant after the filter residue and drying washed and make the additive of cement.
Equally, the phosphorus in system material also can be oxidized by nitric acid into phosphoric acid.Filtrate after above-mentioned filtration first carries out evaporation and concentration, meeting
After the sour gas use water sent out absorbs, form acid solution, return again to workshop after reaching certain concentration and use.After being finally evaporated,
Metallic salt mixture can be obtained, it is tested, carry out separating, purifying according to test result, the most available
Corresponding highly purified metal.
Claims (10)
1. the technique preparing gas-phase silica for raw material with quartziferous fluorite mine tailing, it is characterised in that include following step
Rapid: (1), by fluorine-containing acid solution, mix with one or both in nitric acid, hydrochloric acid, prepare mix acid liquor standby；Will
Quartziferous fluorite mine tailing is ground to the fineness of below 200 mesh, with magnet separator magnetics more than 10000 Gausses in grinding process
Blanking ferrum, prepares powder；
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
Device, puts into powder in reactor；
(3), the reaction temperature controlled in reactor be 70～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and quartz
Silicon dioxde reaction in matter fluorite mine tailing generates silicon tetrafluoride gas, is volatilized in this silicon tetrafluoride gas and mix acid liquor
Sour gas and steam brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 0～36 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 can
For reusable Fluohydric acid., hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects
SiO in cooling reactor2·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 gas-phase silica product after drying, SiO in product2
Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), in a kettle., mix acid liquor is oxidized to sulphuric acid the sulfur component in powder, after reaction kettle for reaction completes,
Filtered while hot, obtains filtering residue and filtrate, washes filtering residue with water neutrality, sells or be used as after the filter residue and drying washed
Cement adds material；Or filtering residue is carried out flotation again, i.e. can get highly purified Fluorspar Powder and borontrifluoride aluminium powder.
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: described Fluohydric acid.
Mass concentration or volumetric concentration are 1～20%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, the matter of nitric acid
Amount concentration or volumetric concentration are 2～30%, and the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%.
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: by system in step (1)
Powder with acid solution washing remove calcium, after, then after removing acid solution washing material, last processed.
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: step (6) filters
After filtrate first carry out evaporation and concentration, after the sour gas use water of volatilization absorbs, form acid solution, return again to workshop and use；
After filtrate being finally evaporated, metallic salt mixture can be obtained, metallic salt mixture be tested, according to test
Result carries out separating, purifying, and i.e. can get corresponding metal.
5. the device in technique described in claim 1, it is characterised in that: described device includes that hot-air send
Entering system, chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air feeding system is used for storing pressure
Contracting air and send into after air is heated chemical reaction system and in；Described chemical reaction system is by acid solution storage tank, material
Storehouse and reactor composition, acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin, is provided with and stirs in reactor
Mixing device, the liner of reactor is heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular
Pipe, pipe is evenly distributed with air-vent or permeability cell, be provided with in reactor more than one with annular pipe
The vertical tube being connected, the top of described vertical tube is sent into system by the pipe valve on the kettle cover of reactor with hot-air and 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, this tube bank
Cold and hot medium outside two ends are respectively with still wall up and down is connected by its valve, by being passed through cold and hot Jie to the capillary tube in restraining
Matter, 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,
The kettle cover of reactor is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center, one-level with one-level cooling reactor
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 the pipeline for two grades of cooling reactor bottom center that is connected with two grades of cooling reactors and is deep into, two grades of described cooling reactors
Be internally provided with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；It is provided with on the kettle cover of two grades of cooling reactors
A piece pipeline being connected with waste gas absorbing system, described waste gas absorbing system by more than one negative pressure water tourie and
Acid mist absorbing device forms, and the top of negative pressure water tourie is provided with pipeline and by pipeline and drawing in acid mist absorbing device
Blower fan is connected.
Device the most according to claim 5, it is characterised in that: described hot-air is sent into system and is included air pressure
Contracting machine, air storage tank, air heater and pipeline, air compressor, air storage tank and air heater pass through
Pipeline is connected, and pipeline is additionally provided with valve and instrument.
Device the most according to claim 5, it is characterised in that: be evenly distributed with on described pipe a diameter of 10～
20mm's and towards different permeability cells, the adjacent spacing between permeability cell is 50～150mm, and adjacent ventilative
The angle stretched out between direction of pipe is 60～120 °, is provided with two vertical tubes in reactor, and described two vertical tubes are respectively
It is connected to the two ends, left and right of pipe.
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 cold
But disk composition, described rotating shaft is the hollow circular-tube that an outer wrap has politef, and the top of rotating shaft is cold by one-level
But stretching out on the kettle cover of still, be provided with a top-down cooling water pipe A in rotating shaft, the top of cooling water pipe A is for entering
Water end (W.E.) and water inlet end are connected with cooling water source；Being evenly distributed with cooling disk in rotating shaft, described cooling disk with rotating shaft is
The center of circle is fixed in rotating shaft, and rotates with rotating shaft, and described cooling disk is hollow structure, all cooling disks interior
Portion is provided with the cooling water pipe B head and the tail phase in the cooling water pipe B of distribution in spiral shape, and neighbouring cooling disk
Even, the water inlet end of cooling water pipe B in the cooling disk of bottommost is connected with the bottom of cooling water pipe A, top
Cooling disk in the water side of cooling water pipe B lead to hollow circular-tube, the cooling water discharged in cooling water pipe B is by turning
The top of axle is overflowed；It is evenly distributed with on vertical passage, and neighbouring cooling disk on described cooling disk
Passage mutual dislocation.
Device the most according to claim 8, it is characterised in that: the kettle cover of described one-level cooling reactor is provided with very
Empty table and the manhole of easy access, the kettle cover of one-level cooling reactor is additionally provided with compressed air blowning installation, and compressed air is blown
Device of air is connected with compressed gas source.
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 with
The water inlet of lower floor's fin is connected, and cooling water is flowed into by undermost fin, and described fin is Curved Continuous folded structure, phase
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；Two grades of coolings
Being provided with compressed air blowning installation on the kettle cover of still, compressed air blowning installation is connected with compressed gas source, and two grades cold
But the kettle cover of still is provided with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.
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| CN107445655A (en) * | 2017-08-25 | 2017-12-08 | 河南绿能环保科技有限公司 | From the technique of fluorite pulp thickening siliceous fertilizer |
| CN108439452A (en) * | 2018-04-28 | 2018-08-24 | 湖南有色氟化学科技发展有限公司 | A kind of purifying technique of low-grade fluorite |
| CN110575801A (en) * | 2018-06-11 | 2019-12-17 | 河南骏化发展股份有限公司 | Multifunctional alternating load reaction kettle for preparing white carbon black by double-salt double decomposition method |
| CN111960456A (en) * | 2020-08-06 | 2020-11-20 | 六盘水师范学院 | Recycling and treating process for calcium-containing waste acid after acid leaching of fluorite |
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