CN105967192A - Process and device for preparing gas-phase white carbon black and recycling metal by taking industrial waste residues containing silicate as raw materials - Google Patents
Process and device for preparing gas-phase white carbon black and recycling metal by taking industrial waste residues containing silicate as raw materials Download PDFInfo
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- CN105967192A CN105967192A CN201610534965.8A CN201610534965A CN105967192A CN 105967192 A CN105967192 A CN 105967192A CN 201610534965 A CN201610534965 A CN 201610534965A CN 105967192 A CN105967192 A CN 105967192A
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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
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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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
Abstract
The invention provides a process for preparing gas-phase white carbon black at a low temperature and recycling metal by taking industrial waste residues containing silicate as raw materials. In the process, wastes including the industrial waste residues 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 the metal is 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 industrial residue with silicate as raw material, prepare gas-phase silica the technique reclaiming metal
Method and device, belongs to chemical industry and purifies and environmental technology field.
Background technology
Since reform and opening-up, China, while science and technology achieves huge advance, economically have also been obtained quickly
Development；It is in particular in that the aspects such as mining, metal smelt, coal-fired power plant, chemical industry, building materials also obtain quickly
Development；During industrial development, also discharged substantial amounts of industrial residue: such as: copper ashes, slag, nickel slag, sulphuric acid simultaneously
Aluminum slag, lithium slag, blast-furnace cinder, ferroalloy slag, lead cadmia, granulation circuit phosphorus slag etc.；Also have nonmetallic ore waste residue: as,
The mineral such as Kaolin, Anhydrite, Talcum, pyrophyllite, bentonite, attapulgite, Paligorskite, serpentine, wollastonite give up
Slag；And the main component in these waste residues be iron sesquioxide, silicon dioxide, aluminium sesquioxide, calcium oxide, magnesium oxide,
Potassium oxide, sodium oxide and the non-ferrous metal such as gold, silver, copper thereof.The data provided according to national statistics department: industry in 2004
Waste residue is 1,200,000,000 tons, within 2009, breaks through 2,000,000,000 tons ...；These industrial residues are not if utilized, on the one hand: store up in a large number
Do not only take up substantial amounts of soil, also result in serious atmospheric pollution, soil pollution and water resource pollution, present environmental risks
And human health, have become as the big public hazards during social development.On the other hand, industrial residue is again a kind of secondary
Resource, has the biggest value, if industrial residue is carried out innoxious and recycling treatment, carries out secondary resource
Science, rationally, utilize efficiently, our society is carried out energy-saving and emission-reduction, environmental protection, the sum of Man & Nature by this
Humorous development has highly important realistic meaning.
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.
If industrial residue can be carried out secondary operations utilization, it is combined with the preparation of gas-phase silica, be used for making
Standby gas-phase silica product, then will solve the thorny technical problem of above-mentioned two in this area, has the most progressive.
Summary of the invention
The invention provides a kind of industrial residue with silicate as raw material, prepare fume colloidal silica and reclaim metal
Manufacturing technique method and device；It successfully avoids and uses hydrogen and oxygen and high temperature now during fume colloidal silica
The technical process of hydrolysis, also solves the problem that current industrial residue can not efficiently utilize, and the present invention additionally provides simultaneously
Novel technique and the process units of gas-phase silica product can be produced at normal temperatures and pressures.
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 industrial residue, 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 industrial residue
Being ground to the fineness of below 200 mesh, magnetic separation removes ferrum therein, and the material oar after magnetic separation and gravity treatment is concentrated and after dehydration
Prepare silicate breeze and analyze its SiO2、Al2O3、CaO、MgO、K2O、Na2After the content of O standby；If alkali
Metal or alkaline earth metal content are high, after the most first removing with concentrated hydrochloric acid is molten, filter, wash filtering residue, dehydration after standby；Filtrate is single
Stay alone reason；
(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 the material in step (1) in reactor；
(3), the reaction temperature controlled in reactor be 75～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and industry
Silicon dioxde reaction in waste residue generates the salt volatilized in silicon tetrafluoride gas, this silicon tetrafluoride gas and mix acid liquor
The sour gas such as acid, nitric acid and steam are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 10～40 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) silicon dioxide during, in a kettle., fluorine-containing acid solution decomposes silicate breeze and aluminium sesquioxide；Hydrochloric acid with
Residual metallic in nitric acid then decomposing materials, the metal after decomposition is stayed in mix acid liquor with the form of ion and salt；Reaction
Material reaction in still filters after completing, and isolates the AlF in filtering residue3；Then filtrate is sent in vaporizer and is evaporated,
The acid mist gas produced in evaporation process, recycles after absorbing certain concentration by water；I.e. can get metallic salt to mix
Compound, then isolate various metal by displacement reaction.
The mass concentration of described Fluohydric acid. or volumetric concentration are 2～30%, and the mass concentration of hexafluosilicic acid or volumetric concentration are
10～30%, the mass concentration of nitric acid or volumetric concentration are 2～40%, the mass concentration of hydrochloric acid or volumetric concentration be 10%～
30%.
The acid mist gas gas water tourie produced during evaporation in step (6) carries out absorption and becomes acid solution, when acid solution reaches
After finite concentration, returning again to workshop and re-use, unabsorbed tail gas acid fog absorption tower empties after being neutralized process.
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 synthesis system after row heating；Described synthesis system is made up of acid solution storage tank, feed bin and reactor, acid solution storage tank and
The bottom of feed bin is connected with reactor by pipeline, is provided with agitating device in reactor, the liner of reactor be heatproof,
Acidproof, high-abrasive material, bottom reactor above, be provided with an annular pipe, pipe be evenly distributed with ventilative
Hole or permeability cell, be provided with the vertical tube that the pipe with annular of more than is connected, the top of described vertical tube in reactor
Send into system by the pipe valve on the kettle cover of reactor with hot-air to be connected；Still inwall is installed from top to bottom or from bottom to top
Have 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 outside cold and hot Jie
Matter is connected by its valve, by give tube bank in capillary tube be passed through cold and hot medium, in still response system provide heating or
Cooling.
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 industrial residue
The like waste, as raw material, is prepared into the product gas phase white carbon of high added value, SiO in obtained product2Contain
Amount is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 350m2/ g, has therefore reached the effect turned waste into wealth
Really.2, preparation technology provided by the present invention belongs to a kind of brand-new technique thinking, solves existing gas-phase silica
High-temperature process in the presence of preparation technology, use the shortcomings such as breakneck inflammable and explosive hydrogen and oxygen.The present invention
The production technology provided can be prepared at normal temperatures and pressures.3, produced acid in the preparation technology of the present invention
Gas is after negative pressure water tourie absorbs, it is possible to prepare corresponding acid solution, capable of circulation after acid solution is concentrated to certain concentration
Use, it is possible to greatly saved the cost in producing and the problem of environmental protection treatment waste water.4, the production that the present invention provides
Device is capable of large-scale industrial production, and used parts are chemical plant common tool, with low cost.
5, the present invention can reclaim for the high-valency metal in industrial residue, 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,
Synthesis system, cooling system and waste gas absorbing system, wherein hot-air sends into system for storing compressed air and to sky
Gas is sent in synthesis system after heating, and described hot-air is sent into system and included air compressor 12, air storage tank
13, air heater 14 and pipeline, air compressor 12, air storage tank 13 and air heater 14 are by pipe
Road is connected, 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 industrial residue that Hubei mining company is produced, the detailed preparation technology of the present invention is done in detail below
Illustrating, through analyzing, in this industrial residue, each constituent content is as follows: SiO2: 30.73%；Al2O3: 1.32%, Fe2O3:
5.95%；CaO:50.65%；K2O:0.08%；MgO:11.30%；SO3: 0.10%；Na2O:0.10%.
Concrete production stage is as follows:
(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 2～30%, the mass concentration of hexafluosilicic acid or volume
Concentration is 10～30%, and the mass concentration of nitric acid or volumetric concentration are 2～40%, the mass concentration of hydrochloric acid or volumetric concentration
It is 10%～30%.
Industrial residue is ground to the fineness of below 200 mesh, and magnetic separation removes ferrum therein, the material oar after magnetic separation and gravity treatment
Preparing silicate breeze after concentrated and dehydration standby, silicate breeze uses optimal after drying, but to increase corresponding cost.
(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 silicate breeze 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 75～85 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 industrial residue, and this gas part is dissolved in the water of reaction system
Form hexafluosilicic acid and continue to dissolve the silicon dioxide in industrial residue, the silicon tetrafluoride gas of another part spilling and the nitre of volatilization
Acid/HCl gas and steam are brought in cooling reactor by negative pressure together.
(4), the chilling temperature controlled in cooling reactor be 10～40 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: Fluohydric acid. and hexafluosilicic acid decompose the silicon dioxide and three in silicate breeze
Al 2 O；Hydrochloric acid and other metals in nitric acid then decomposing materials, alkali metal；Nitric acid primarily serves oxygen in the process
Change effect, hydrochloric acid complexing.Metal after decomposition is then stayed in acid solution with ion and corresponding salt；Take advantage of after having reacted
After heat filtering, being mainly composed of in filtering residue: AlF3、TiO2, then the titanium ore in molten for filtering residue concentrated sulphuric acid slagging-off is used for
Prepare titanium dioxide raw material；It is finally separating out AlF3Product；Filtrate is sent into evaporator evaporation while hot and is evaporated, i.e. available height
Simple metal salt (rare earth metal) mixture；The content of various valuable metal elements in analysis of mixtures again, further according to analysis
Result by replacing, neutralize, extract, the various metal of means separation and Extraction such as recrystallization: as, gold, silver, copper and rare earth
Element etc.；The acid mist gas gas water tourie produced during evaporation carries out more than two grades absorptions and becomes acid solution, when acid solution reaches
After finite concentration, returning again to workshop and re-use, unabsorbed tail gas acid fog absorption tower empties after being neutralized process.
Claims (10)
1. prepare gas-phase silica with the industrial residue of silicate for raw material and reclaim a technique for metal, its feature
It is to comprise the following steps: (1), by fluorine-containing acid solution, mixes with one or both in nitric acid, hydrochloric acid, prepare mixed
Conjunction acid solution is standby；Industrial residue is ground to the fineness of below 200 mesh, and magnetic separation removes ferrum therein, through magnetic separation and gravity treatment
After material oar concentrated and dehydration after prepare silicate breeze analyze its SiO2、Al2O3、CaO、MgO、K2O、Na2O
Content after standby；If alkali metal or alkaline earth metal content are high, after the most first removing with concentrated hydrochloric acid is molten, filter, wash filtering residue,
After dehydration standby；Filtrate individual processing；
(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 the material in step (1) in reactor；
(3), the reaction temperature controlled in reactor be 75～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and industry
Silicon dioxde reaction in waste residue generates silicon tetrafluoride gas, the acidity will volatilized in silicon tetrafluoride gas and mix acid liquor
Gas and steam are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 10～40 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) silicon dioxide during, in a kettle., fluorine-containing acid solution decomposes silicate breeze and aluminium sesquioxide；Hydrochloric acid with
Residual metallic in nitric acid then decomposing materials, the metal after decomposition is stayed in mix acid liquor with the form of ion and salt；Reaction
Material reaction in still filters after completing, and isolates the AlF in filtering residue3；Then filtrate is sent in vaporizer and is evaporated,
I.e. can get high pure metal salt mixture, each metal in metal mixture is given respectively separation and Extraction, i.e. can get not
Same high purity metal.
The most according to claim 1 prepare gas-phase silica the technique reclaiming metal, it is characterised in that: described
The mass concentration of Fluohydric acid. or volumetric concentration be 2～30%, the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%,
The mass concentration of nitric acid or volumetric concentration are 2～40%, and the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%.
The most according to claim 1 prepare gas-phase silica the technique reclaiming metal, it is characterised in that: step
(6) the acid mist gas gas water tourie produced during evaporation in carries out absorption and becomes acid solution, when acid solution reaches finite concentration
After, returning again to workshop and re-use, unabsorbed tail gas acid fog absorption tower empties after being neutralized process.
4. 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 4, 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 4, 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 4, 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 7, it is characterised in that: a diameter of the 10 of described passage～20mm,
The adjacent centre-to-centre spacing between passage is 20mm～30mm.
Device the most according to claim 7, 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 4, 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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| CN114085553A (en) * | 2021-12-07 | 2022-02-25 | 无锡恒诚硅业有限公司 | Device and method for producing high-dispersion white carbon black |
| CN114507902A (en) * | 2022-01-26 | 2022-05-17 | 陕西理工大学 | Nano silicon nitride crystal whisker and preparation method thereof |
| CN115819008A (en) * | 2023-02-20 | 2023-03-21 | 西南交通大学 | High-activity and low-shrinkage composite mineral admixture and preparation method thereof |
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| CN105967192B (en) | 2020-03-24 |
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