CN106219560A - A kind of technique and device preparing gas-phase silica with quartz for raw material low temperature - Google Patents
A kind of technique and device preparing gas-phase silica with quartz for raw material low temperature Download PDFInfo
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- CN106219560A CN106219560A CN201610536865.9A CN201610536865A CN106219560A CN 106219560 A CN106219560 A CN 106219560A CN 201610536865 A CN201610536865 A CN 201610536865A CN 106219560 A CN106219560 A CN 106219560A
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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
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/40—Preparation by absorption of oxides of nitrogen
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
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- 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 kind of technique preparing gas-phase silica for raw material low temperature with quartz, using quartz tail sand or micropowder the like waste as raw material in this technique, it is reacted with fluorine-containing acid solution, hydrochloric acid and nitric acid, is prepared as the product gas phase white carbon of high added value, SiO in obtained product2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is: 350～500m2/ g, has reached the effect turned waste into wealth；In above-mentioned preparation technology, produced sour gas is after negative pressure water tourie absorbs, it is possible to prepares corresponding acid solution, can be recycled after acid solution is concentrated to certain concentration.Present invention also offers the process units in above-mentioned technique, the parts used in this process units are chemical plant common tool, with low cost, it is possible to realize large-scale industrial production simultaneously.
Description
Technical field
The present invention relates to one utilizes quartz sand, quartz tail sand (micropowder) low temperature to prepare the technique side that gas-phase silica produces
Method and device, belong to chemical industry and purify and environmental technology field.
Background technology
Quartz tail sand is the garbage in quartz sand process of manufacture.At present China's quartz sand process of manufacture produces
Raw tailings is annual all in terms of ten million ton, the most effectively solves the secondary Utilizing question of quartz tail sand resource, some quartz sands
Manufacturing enterprise starts to produce aerated bricks and materials for wall with quartz tail sand；Also some enterprises are had to sell cement plant, ceramics factory it
Make siliceous raw material；The powder body also having some enterprises that it is worn into 325 mesh does low-grade silicon powder raw material；Above-mentioned several practice, does not all have
Quartz tail sand is made to obtain effective and efficient, science and reasonably utilize.To this end, with quartz tail sand as raw material, develop high skill
Art content, high value added product, be not only the expectation that each quartz sand manufacturing enterprise is the most eager, is also that every silicon materials grind simultaneously
One challenging problem of the personnel of sending out.
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 gasify (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
Fume colloidal silica granule is superfine, forms aerosol with gas, is difficult to trapping, therefore makes it first be gathered into bigger in collector
Grain, then through cyclone collection, is re-fed into deacidification furnace, is 4～6 i.e. with nitrogenous air blowing aerosil to pH value
For finished product.China produces the enterprise of gas-phase silica at present and mostly uses this method, and this method is also the most general gas phase Linesless charcoal
Black production method.Ye You enterprise of China uses methyl trichlorosilane to produce gas-phase silica, and have successfully completed industrialization
Produce.The production technology of fume colloidal silica now does not only exist high-temperature process, but also uses breakneck and easy
Firing explosive hydrogen and oxygen, in its production process, the operating environment of workman is arduouser；Safety coefficient is required the highest.Consult
Related data and Chinese patent literature, do not find to utilize the relevant report of other raw material production gas-phase silicas.
If quartz tail sand can be carried out secondary operations utilization, it is combined with the preparation of gas-phase silica, is used for
Prepare gas-phase silica 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 a kind of with quartz sand, quartz tail sand or quartz micropowder as raw material, prepare the life of gas-phase silica
Production. art and device；It successfully avoids during vapor phase method prepares white carbon now and uses hydrogen and oxygen and pyrohydrolysis
Technical process, the present invention additionally provides novel technique and the life that can produce gas-phase silica product at normal temperatures and pressures simultaneously
Produce device.
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 low temperature with quartz, it is characterised in that comprise the following steps: (1),
By one or both in Fluohydric acid., hexafluosilicic acid, mix with one or both in nitric acid, hydrochloric acid, prepare mix acid liquor；
(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 quartz sand, quartz tail sand or quartz micropowder in reactor；
(3), the reaction temperature controlled in reactor be 75～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and quartz
Sand, quartz tail sand or quartz micropowder reaction generation silicon tetrafluoride gas, volatilized in this silicon tetrafluoride gas and mix acid liquor
The sour gas such as nitric acid, hydrochloric acid and steam are 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 and is generated HF, Cl2/
NO2、SiO2·nH2O, wherein HF and Cl2/NO2Taken out of in 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 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 product2Content is more than
99.9%, its multiple spot BET method measurement the specific area is: 350～500m2/g。
The mass concentration of described Fluohydric acid. or volumetric concentration are 10～20%, the mass concentration of hexafluosilicic acid or volumetric concentration
Being 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%.
Present invention also offers the device in above-mentioned technique, described device includes that hot-air sends into system, chemistry instead
Answering 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, and acid solution is stored up
Tank is connected with reactor by pipeline with the bottom of feed bin, is provided with agitating device in reactor, and the liner of reactor is resistance to
Warm, acidproof, high-abrasive material, bottom reactor above, be provided with an annular pipe, pipe be evenly distributed with air-vent
Or permeability cell, it being provided with the vertical tube that the pipe with annular of more than is connected in reactor, the top of described vertical tube is passed through
Pipe valve on the kettle cover of reactor is sent into system with hot-air and is connected；Still inwall is provided with from top to bottom or from bottom to top to be close to
Still wall and the tetrafluoro bundle of capillary tubes of helically wire, the two ends up and down of this tube bank respectively with still wall outside cold and hot medium by it
Valve connects, and by being passed through cold and hot medium to the capillary tube in restraining, provides heating or cooling for response system in still.
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.
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
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.
Described negative pressure water tourie is provided with two, and two negative pressure water touries are in series or are connected in parallel.
Applicant of the present invention is with quartz tail sand as raw material, during research and development high technology content and high value added product,
Finding that quartz tail sand, after reacting with Fluohydric acid. or hexafluosilicic acid, generates silicon tetrafluoride gas, this gas, in volatilization process, is being met
Under conditions of steam and volatile acid solution gas (example hydrochloric acid, nitric acid or hydrochloric acid and the mixed acid etc. of nitric acid), at room temperature
Spherical granular hydrated silica can be generated under conditions of cooling.Through experimental verification the most repeatedly, this Technology is feasible, energy
Enough carrying out industrialized production, corresponding applicant also develops the process units of its correspondence.
Compared with prior art, technical scheme provided by the present invention has the advantage that 1, the present invention is with quartz tail sand
Or micropowder the like waste is as raw material, is prepared into the product gas phase white carbon of high added value, SiO in obtained product2
Content is more than 99.9%, and its multiple spot BET method measurement the specific area is: 350～500m2/ 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 and prepares
High-temperature process in the presence of technique, use the shortcomings such as breakneck inflammable and explosive hydrogen and oxygen.Provided by the present invention
Production technology can be prepared at normal temperatures and pressures.3, produced by the preparation technology of the present invention, sour gas is through negative pressure
After water tourie absorbs, it is possible to prepare corresponding acid solution, can be recycled after acid solution is concentrated to certain concentration, it is possible to significantly
Saving produce in cost and the problem of environmental protection treatment waste water.4, the process units that the present invention provides is capable of on a large scale
Industrialized production, 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 quartz tail sand that Hubei mining company is produced, the detailed preparation technology of the present invention is done in detail below
Describing in detail bright, 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, hexafluosilicic acid, nitric acid or hydrochloric acid are technical grade；Or use industrial by-product.As preferably, described
The mass concentration of Fluohydric acid. or volumetric concentration be 10～20%, 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%.
(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 quartz tail sand or quartz micropowder in reactor；In actual production, quartz sand is of course also possible
, but it is relatively costly, uses uneconomical, therefore uses quartz tail sand or quartz micropowder in the present embodiment.
(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 mix acid liquor put into
In do not contain Fluohydric acid. and containing hexafluosilicic acid, then need the steam opening reacting kettle jacketing slowly to heat to reactor.Mix acid liquor
In Fluohydric acid. or hexafluosilicic acid and quartz sand, quartz tail sand or quartz micropowder react generation silicon tetrafluoride gas, this gas one
Dividing to be dissolved in the water of reaction system and form the silicon dioxide in hexafluosilicic acid continuation dissolving quartz tail sand (powder), another part overflows
Send in cooling reactor together with the nitric acid/HCl gas of silicon tetrafluoride gas and volatilization and steam.
(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor and is generated 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 by negative pressure from one-level cooling reactor and two grades of cooling reactors, 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 gas-phase silica product after drying, in product
SiO2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is: 350～500m2/g。
Claims (10)
1. the technique preparing gas-phase silica for raw material low temperature with quartz, it is characterised in that comprise the following steps: (1), general
One or both in Fluohydric acid., hexafluosilicic acid, mix with one or both in nitric acid, hydrochloric acid, prepare mix acid liquor；
(2), mix acid liquor is put in reactor, the waste gas absorption dress in the agitating device of unlatching reactor and response system
Put, quartz sand, quartz tail sand or quartz micropowder are put in reactor；
(3), the reaction temperature controlled in reactor be 75～85 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and quartz sand,
Quartz tail sand or quartz micropowder reaction generate the nitre volatilized in silicon tetrafluoride gas, this silicon tetrafluoride gas and mix acid liquor
The sour gas such as acid, hydrochloric acid and steam are admitted in cooling reactor by tiny structure together；
(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor and is generated HF, Cl2/NO2、
SiO2·nH2O, wherein HF and Cl2/NO2Taken out of cooling reactor by negative pressure, and be only absorbed by the water generation be available for reusable Fluohydric 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: 350～500m2/g。
The technique that low temperature the most according to claim 1 prepares gas-phase silica, it is characterised in that: the matter of described Fluohydric acid.
Amount concentration or volumetric concentration are 10～20%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, and the quality of nitric acid is dense
Degree or volumetric concentration are 2～40%, and the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%.
3. the device prepared for low temperature described in claim 1 in the technique of gas-phase silica, it is characterised in that: described
Device includes that hot-air sends into system, chemical reaction system, cooling system and waste gas absorbing system, and wherein hot-air sends into system
System for storing compressed air and send into after air is heated chemical reaction system and in；Described chemical reaction system is by acid
Liquid storage tank, feed bin and reactor composition, acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin, sets in reactor
Being equipped with agitating 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 phase
The vertical tube of connection, 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；In still
Wall 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, up and down the two of this tube bank
Cold and hot medium outside holding respectively with still wall is connected by its valve, by being passed through cold and hot medium, for still to the capillary tube in restraining
Interior response system provides 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, 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 3, 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 3, 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 3, it is characterised in that: the chiller of described one-level cooling reactor is by rotating shaft and cooling
Disk forms, and described rotating shaft 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 A in rotating shaft, the top of cooling water pipe A is water inlet end and enters
Water end (W.E.) is connected with cooling water source；Being evenly distributed with cooling disk in rotating shaft, described cooling disk is installed solid with rotating shaft for the center of circle
Being scheduled in rotating shaft, and rotate with rotating shaft, described cooling disk is hollow structure, and the inside of all cooling disks is provided with in dish
Cooling water pipe B in the cooling water pipe B of rotation shape distribution, and neighbouring cooling disk joins end to end, the cooling circle of bottommost
The water inlet end of the cooling water pipe B in dish is connected with the bottom of cooling water pipe A, the cooling water pipe B in the cooling disk of top
Water side lead to hollow circular-tube, in cooling water pipe B discharge cooling water by rotating shaft top overflow；On described cooling disk
It is evenly distributed with the passage mutual dislocation on vertical passage, and neighbouring cooling disk.
Device the most according to claim 6, it is characterised in that: a diameter of the 10 of described passage～20mm, adjacent is logical
Centre-to-centre spacing between pore is 20mm～30mm.
Device the most according to claim 6, 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 3, it is characterised in that: the described chiller in two grades of cooling reactors is multilamellar wing
Chip architecture, the still wall of two grades of cooling reactors is provided with cooling water inlet and coolant outlet, cooling water inlet and orlop fin
Water inlet be connected, cooling water flowed into by undermost fin, described fin is Curved Continuous folded structure, adjacent two-layer up and down
The end of fin is connected, and coolant outlet is connected with the outlet of the superiors' fin；Arrange on the kettle cover of two grades of cooling reactors
Having compressed air blowning installation, compressed air blowning installation to 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 be designed with the manhole of easy access.
Device the most according to claim 3, it is characterised in that: described negative pressure water tourie is provided with two, bears for two
Setting-out tourie is in series or is connected in parallel.
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| CN201610536865.9A CN106219560B (en) | 2016-07-08 | 2016-07-08 | It is a kind of with quartz be raw material low temperature preparation gas-phase silica technique and device |
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| CN201610536865.9A CN106219560B (en) | 2016-07-08 | 2016-07-08 | It is a kind of with quartz be raw material low temperature preparation gas-phase silica technique and device |
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| CN106219560B CN106219560B (en) | 2018-11-13 |
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| WO2012044349A2 (en) * | 2010-10-02 | 2012-04-05 | Matthew James Channon | Fluorspar/iodide process for silicon purification |
| CN102586632A (en) * | 2012-02-22 | 2012-07-18 | 中南大学 | Method for comprehensively recovering tungsten and fluorine from minerals |
| CN103601195A (en) * | 2013-10-14 | 2014-02-26 | 班仁义 | Gas phase hydrolysis and fluoride-silicon separation method of silicon tetrafluoride |
| CN104843712A (en) * | 2015-04-24 | 2015-08-19 | 北京化工大学 | Industrial fluosilicic acid purification and white carbon black co-production method |
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| CN1458061A (en) * | 2003-04-13 | 2003-11-26 | 季海水 | Process for extracting CaF2 and SiO2 from fluorite tailing and producing fluorosilicic acid further |
| CN101774587A (en) * | 2010-02-11 | 2010-07-14 | 浙江中宁硅业有限公司 | Method for preparing silicon tetrafluoride by quartz sand |
| WO2012044349A2 (en) * | 2010-10-02 | 2012-04-05 | Matthew James Channon | Fluorspar/iodide process for silicon purification |
| 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 |
| CN102586632A (en) * | 2012-02-22 | 2012-07-18 | 中南大学 | Method for comprehensively recovering tungsten and fluorine from minerals |
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