CN106219558B - A kind of technique and device preparing gas-phase silica as raw material using gold tailings and recycle metal - Google Patents
A kind of technique and device preparing gas-phase silica as raw material using gold tailings and recycle metal Download PDFInfo
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- CN106219558B CN106219558B CN201610534980.2A CN201610534980A CN106219558B CN 106219558 B CN106219558 B CN 106219558B CN 201610534980 A CN201610534980 A CN 201610534980A CN 106219558 B CN106219558 B CN 106219558B
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of techniques for preparing gas-phase silica as raw material using gold tailings and recycling metal, using gold tailings the like waste as raw material in the technique, it is reacted with fluorine-containing acid solution, hydrochloric acid and nitric acid, it is prepared into the product gas phase white carbon of high added value and recycles the metals such as gold, silver, copper, iron, SiO in obtained product2Content is more than 99.9%, and multiple spot BET method measurement the specific area is not less than 350m2/ g has achieved the effect that turn waste into wealth；Generated sour gas can be made corresponding acid solution, can be recycled after acid solution is concentrated to certain concentration after the absorption of negative pressure water tourie in above-mentioned preparation process.Simultaneously the present invention also provides for the process units in above-mentioned technique, the parts used in the process units are chemical plant common tool, of low cost, can realize large-scale industrial production.
Description
Technical field
The present invention relates to a kind of processes and device preparing gas-phase silica using gold tailings and recycle metal, belong to
In chemical industry purification and environmental technology field.
Background technology
According to the 8th phase/34th volume in 2013《Gold》Periodical, safety and environmentally friendly column, Hu Yue, Ding Feng, Liu Tao, Ke Jianping,
What Liu Na etc. was delivered《Gold mine tailing comprehensive utilization technique is studied and applies new development》One text is introduced：The Huang in China in 2012
Golden yield breaches 400 tons of high pointes, reaches 403.047 tons, increases by 11.66% on a year-on-year basis, then record high, and occupies within continuous 6 years
The first in the world.But a large amount of tailings generated during golden production are the problem of meriting attention, tailings glass is also to restrict
One of the principal element of gold industry sustainable development, be particularly due to the production technology level before the 1990s it is low, enterprise
Industry extensive management so that contain a large amount of valuable metal and available resources in gold tailings.According to statistics according to imperfect number
Show that Chinese gold industry industry is annual and generates more than 2 000 ten thousand tons of tailing amount.Contain harmful substance in gold tailings, in stacking process
In do not only take up large area soil, can also influence the environment of surrounding；Moreover, in tailing containing a large amount of valuable metal (gold, silver,
Iron, copper etc.), therefore recycled tailing as secondary resource, paid much attention to by gold manufacturing enterprises.
Currently, the comprehensive utilization of gold tailings mainly has 3 kinds of methods：1. using tailing as mineral metal products secondary resource, carry
Fetch the valuable metal in ending mine；2. can be selected according to the different component of tailing using tailing as nonmetal mineral resource
Different methods are recycled tailing；3. by gold tailings for producing construction material and backfilling material etc..
Although the method for above-mentioned introduction can effectively the metalliferous mineral in gold tailings, that nonmetallic mineral carries out part is effective
Recycling and utilization, and preferable effect can be obtained；But see that there is also comprehensive utilization ratio is not high from efficient utilize of tailing
Problem is mainly manifested in：1, precious metal element is not adequately recycled and is utilized；2, nonmetallic mineral does not obtain maximum
The utilization of change；3, value-added content of product is not high during recycling.
Invention content
The present invention provides one kind using gold tailings as raw material, prepares gas-phase silica and recycles the gold such as gold, silver, copper, iron
The technique and device of category；It successfully avoids during vapor phase method now prepares white carbon and uses hydrogen and oxygen and high-temperature water
The technical process of solution, also solves the problem of current gold tailings cannot be utilized efficiently, and the present invention is additionally provided normal simultaneously
The novel technique and process units of gas-phase silica product can be produced under normal temperature and pressure.
Technical solution is used by realizing above-mentioned purpose of the present invention：
A kind of technique for preparing gas-phase silica as raw material using gold tailings and recycling metal, it is characterised in that including following
Step:(1), it by fluorine-containing acid solution, is mixed with one or both of nitric acid, hydrochloric acid, it is spare that mix acid liquor is made；By gold
Tailing wears into 200 mesh of grain size hereinafter, the magnetic separation in ore grinding, with recycling iron powder and heavy metal；Slurry after magnetic separation is sent into concentrator
It is spare that gold tailings powder is made after precipitation, then after being dehydrated with ceramic filter；
(2), mix acid liquor is put into reaction kettle, opens the waste gas absorption in the agitating device and reaction system of reaction kettle
Device puts into gold tailings powder in reaction kettle；
(3), it is 70~85 DEG C to control the reaction temperature in reaction kettle, the hydrofluoric acid or fluosilicic acid in mix acid liquor and gold
Silicon dioxde reaction in mine tailing generates silicon tetrafluoride gas, the acidity volatilized in the silicon tetrafluoride gas and mix acid liquor
Gas and vapor are brought by negative pressure in cooling reactor together；
(4), control cooling reactor in cooling temperature be 10~40 DEG C, mixed gas react in cooling reactor generation HF,
Cl2/NO2、SiO2·nH2O, wherein HF and Cl2/NO2It is taken out of from cooling reactor by negative pressure, and is only absorbed by the water generation for repeating to make
Hydrofluoric acid, hydrochloric acid/nitric acid, SiO2·nH2O condensations are adsorbed on the cooling device in cooling reactor, are collected in cooling reactor
SiO2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein remaining acidity
Gas HF and Cl2/NO2, it is then dried again, can be prepared by gas-phase silica product after dry, SiO in product2Content is more than
99.9%, multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), it is filtered after the completion of reaction in reaction kettle, aluminum trifluoride is can be obtained into filter residue after purification, filtrate is sent into
Evaporator evaporates, and the acid mist gas gas that when evaporation generates, which with water tourie absorb, becomes acid solution, and acid solution returns to workshop and weighs again
New to utilize, unabsorbed tail gas empties after being neutralized with acid fog absorption tower；
After the acid solution in evaporator is evaporated, stop evaporation, be washed with water except after the salt in solid residue, then with sulfuric acid pair
Solid residue is handled, after isolating sulfate, finally to its component analysis, according to analysis result, to various metals member
Element carries out purification & isolation recycling.
The mass concentration or volumetric concentration of the hydrofluoric acid are 1~20%, the mass concentration or volumetric concentration of fluosilicic acid
It is 10~30%, the mass concentration or volumetric concentration of nitric acid are 2~30%, the mass concentration or volumetric concentration of hydrochloric acid be 10%~
30%.
Magnetic separation described in step (1) is low middle high three-level wet magnetic separation, specially first uses magnetic field intensity for 3000-
Magnetic separator+jigging machine of 5000 Gausses, then use magnetic field intensity for magnetic separator+jigging machine of 5000-10000 Gausses, finally adopt
With magnetic separator+jigging machine that magnetic field intensity is 10000 Gausses or more.
The gold tailings powder after magnetic separation is handled with concentrated hydrochloric acid in step (1), by alkali metal therein and alkaline earth gold
Belong to and being removed in the form of villaumite, remove acid solution, then spare after progress flotation removing feldspar, the feldspar powder floatingly selected is used as preparation
Ceramic raw material.
The present invention also provides for the device in above-mentioned technique, described device includes that hot-air is sent into system, chemistry instead
Answer system, cooling system and waste gas absorbing system, wherein hot-air be sent into system for storing compressed air and to air into
It is sent into chemical reaction system after row heating；The chemical reaction system is made of acid solution storage tank, feed bin and reaction kettle, acid solution storage
The bottom of tank and feed bin is connected by pipeline with reaction kettle, agitating device is provided in reaction kettle, the liner of reaction kettle is resistance to
Warm, acidproof, wear-resistant material is equipped with an annular pipe, air hole is evenly distributed on pipe in the top of reactor bottom
Or permeability cell, one or more the vertical tube being connected with the pipe of annular is provided in reaction kettle, the top of the vertical tube passes through
Pipe valve on the kettle cover of reaction kettle is sent into system with hot-air and is connected；Kettle inner wall is equipped with from top to bottom or from bottom to top and is close to
Kettle wall and helically linear tetrafluoro bundle of capillary tubes, the upper and lower ends of the tube bank pass through it with the cold and hot medium outside kettle wall respectively
Valve connects, and by being passed through cold and hot medium to the capillary in tube bank, provides and is heated or cooled for reaction system in kettle.
Cooling system is composed in series by level-one cooling reactor and two level cooling reactor；Wherein level-one cooling reactor is connected with reaction kettle
It connecing, the kettle cover of reaction kettle is equipped with a pipeline for being connected with level-one cooling reactor and being deep into level-one cooling reactor bottom center, and one
Grade cooling reactor is internally provided with cooling device, and the bottom of level-one cooling reactor is provided with outlet valve, on the kettle cover of level-one cooling reactor
It is provided with a pipeline for being connected with two level cooling reactor and being deep into two level cooling reactor bottom center, the two level cooling reactor
It is internally provided with cooling device, the bottom of two level cooling reactor is provided with outlet valve；One is provided on the kettle cover of two level cooling reactor
The pipeline being connected with waste gas absorbing system, the waste gas absorbing system are inhaled by more than one negative pressure water tourie and acid mist
Receiving apparatus forms, and is provided with pipeline at the top of negative pressure water tourie and is connected with the air-introduced machine in acid mist absorbing device by pipeline
It connects.
It includes air compressor, air storage tank, air heater and pipeline, air pressure that the hot-air, which is sent into system,
Contracting machine, air storage tank and air heater are connected by pipeline, and valve and instrument are additionally provided on pipeline.
Be evenly distributed on the pipe it is a diameter of 10~20mm's and towards different permeability cells, adjacent permeability cell
Between spacing be 50~150mm, and the angle between the stretching direction of adjacent permeability cell is 60~120 °, is set in reaction kettle
Two vertical tubes are equipped with, two vertical tubes are connected to the left and right ends of pipe.
The cooling device of the level-one cooling reactor is made of shaft and cooling disk, and the shaft is that an outside is enclosed with
The hollow circular-tube of polytetrafluoroethylene (PTFE), the top of shaft are stretched out on the kettle cover by level-one cooling reactor, and one is provided in shaft from upper
The top of cooling water pipe A under and, cooling water pipe A are water inlet end and water inlet end is connected with cooling water source；Uniformly divide in shaft
It is furnished with cooling disk, the cooling disk is fixed on by the center of circle of shaft in shaft, and is rotated with shaft, the cooling circle
Disk is hollow structure, and the inside of all cooling disks is both 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, water inlet end and the cooling water pipe A of the cooling water pipe B in the cooling disk of bottommost
Bottom end be connected, hollow circular-tube is led in the water outlet of the cooling water pipe B in the cooling disk of top, is arranged in cooling water pipe B
The cooling water gone out is overflowed by the top of shaft；It is evenly distributed with vertical venthole on the cooling disk, and neighbouring
Cooling disk on venthole mutual dislocation.
A diameter of 10~20mm of the venthole, the centre-to-centre spacing between adjacent venthole are 20mm~30mm.
The kettle cover of the level-one cooling reactor is equipped with the manhole of vacuum meter and easy access, on the kettle cover of level-one cooling reactor
It is additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.
Cooling device in the two level cooling reactor is multilayer fin structure, is provided on the kettle wall of two level cooling reactor cold
But water inlet and cooling water outlet, cooling water inlet are connected with the water inlet of lowest level fin, and cooling water is by undermost wing
Piece flows into, and the fin is in continuous bending structure, and the end of adjacent upper layer and lower layer fin is connected, cooling water outlet with it is most upper
The water outlet of layer fin is connected；Compressed air blowning installation is provided on the kettle cover of two level cooling reactor, compressed air, which is blown, to be filled
It sets and is connected with compressed gas source, the kettle cover of two level cooling reactor is equipped with vacuum meter, and its kettle cover and bottom are designed with convenient for inspection
The manhole repaiied.
There are two the negative pressure water tourie settings, and two negative pressure water touries are in series or are connected in parallel.
Compared with prior art, technical solution provided by the present invention has the following advantages：1, the present invention is with gold tailings
The like waste is prepared into the product gas phase white carbon of high added value as raw material, SiO in obtained product2Content is big
In 99.9%, multiple spot BET method measurement the specific area is not less than 350m2/ g, therefore achieved the effect that turn waste into wealth.2, this hair
Bright provided preparation process belongs to a kind of completely new technique thinking, solves and is deposited in existing gas-phase silica preparation process
High-temperature process, use the shortcomings of breakneck inflammable and explosive hydrogen and oxygen.Production technology provided by the present invention
It can be prepared at normal temperatures and pressures.3, generated sour gas is inhaled through negative pressure water tourie in preparation process of the invention
After receipts, corresponding acid solution can be made, can be recycled after acid solution is concentrated to certain concentration, can greatly save life
The problem of cost and environmental protection treatment waste water in production.4, process units provided by the invention can realize large-scale industry metaplasia
Production, and used parts are chemical plant common tool, it is of low cost.5, the present invention can be directed in gold tailings
The elements such as gold, silver, copper, iron are recycled, and have prodigious economic benefit.
Description of the drawings
Fig. 1 is the overall structure diagram of preparation facilities provided by the invention；
Fig. 2 is the structural schematic diagram of cooling disk in level-one cooling reactor；
Fig. 3 is the structural schematic diagram of fin in two level cooling reactor；
In figure：1- acid solution storage tanks, 2- feed bins, 3- reaction kettles, 4- agitating devices, 5- pipes, 6- vertical tubes, the cooling of 7- level-ones
Kettle, 8- two level cooling reactors, 9- outlet valves, 10- negative pressure water touries, 11- acid mist absorbing devices, 12- air compressors, 13- are empty
Gas holding vessel, 14- air heaters, 15- shafts, 16- cool down disk, 17- cooling water pipes A, 18- venthole, 19- fins.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment does detailed specific description to the present invention, but protection scope of the present invention
It is not limited to following embodiment.
The structure of preparation facilities provided in the present embodiment as shown in Figure 1, described device includes hot-air be sent into system,
Chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air are sent into system for storing compressed air and right
Air is sent into after being heated in chemical reaction system, and it includes air compressor 12, air storage that the hot-air, which is sent into system,
Tank 13, air heater 14 and pipeline are deposited, air compressor 12, air storage tank 13 and air heater 14 pass through pipeline phase
It connects, valve and instrument is additionally provided on pipeline.
The chemical reaction system is made of acid solution storage tank 1, feed bin 2 and reaction kettle 3, the bottom of acid solution storage tank 1 and feed bin 2
It is connected with reaction kettle 3 by pipeline, is provided with agitating device 4 in reaction kettle 3, the liner of reaction kettle is heatproof, acidproof, wear-resisting
Material specifically selects silicon carbide, fluorine material, graphite material etc..At the top 200mm of 3 bottom of reaction kettle or so place, it is equipped with one
The pipe 5 of annular, a diameter of 100~200mm of the pipe are evenly distributed with a diameter of 10~20mm on the pipe 5
And towards different permeability cells, the spacing between adjacent permeability cell is 50~150mm, and the stretching side of adjacent permeability cell
Angle between is 60~120 °.Two vertical tubes 6 being connected with the pipe of annular, two vertical tubes 6 are provided in reaction kettle
It is connected to the left and right ends of pipe 5, the pipe valve on kettle cover that the top of the vertical tube 6 passes through reaction kettle is sent into hot-air
System is connected.Kettle wall in reaction kettle has spiral hook, is used to support the polytetrafluoroethylene (PTFE) for heating or cooling down in kettle
Bundle of capillary tubes.
Cooling system is composed in series by level-one cooling reactor 7 and two level cooling reactor 8；Wherein level-one cooling reactor 7 and 3 phase of reaction kettle
The kettle cover of connection, reaction kettle 3 is equipped with a pipe for being connected with level-one cooling reactor 7 and being deep into level-one cooling reactor bottom center
Road, level-one cooling reactor 7 are internally provided with cooling device, and the cooling device of the level-one cooling reactor is by shaft 15 and cooling disk
16 compositions, the shaft 15 are the hollow circular-tube that an outside is enclosed with polytetrafluoroethylene (PTFE), and the top of shaft is by level-one cooling reactor
Kettle cover on stretch out, be provided with a top-down cooling water pipe A17 in shaft, the top of cooling water pipe A be water inlet end and
Water inlet end is connected with cooling water source；Cooling disk 16 is evenly distributed in shaft 15.The structure of cooling disk as shown in Fig. 2,
The cooling disk 16 is that the center of circle is fixed in shaft, and is rotated with shaft with shaft 15, and the cooling disk is hollow
The inside of structure, all cooling disks is both provided with the cooling water pipe B of distribution in spiral shape, and in neighbouring cooling disk
Cooling water pipe B join end to end, the water inlet end of the cooling water pipe B in the cooling disk of bottommost and the bottom end phase of cooling water pipe A
It is connected to, hollow circular-tube, the cooling being discharged in cooling water pipe B are led in the water outlet of the cooling water pipe B in the cooling disk of top
Water is overflowed by the top of shaft.Vertical venthole 18, and neighbouring cooling are evenly distributed on the cooling disk
Venthole mutual dislocation on disk, to ensure the cooling effect of its gas.A diameter of 10~20mm of the venthole is adjacent
Venthole between centre-to-centre spacing be 20mm~30mm.
The kettle cover of the level-one cooling reactor is equipped with the manhole of vacuum meter and easy access, on the kettle cover of level-one cooling reactor
It is additionally provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.The kettle cover of level-one cooling reactor 7
On be provided with a pipeline for being connected with two level cooling reactor 8 and being deep into 8 bottom center of two level cooling reactor.The bottom of level-one cooling reactor
Portion is provided with outlet valve 9.
The two level cooling reactor 8 is internally provided with cooling device, and the cooling device in the two level cooling reactor is
Multilayer fin structure, is provided with cooling water inlet and cooling water outlet on the kettle wall of two level cooling reactor 8, cooling water inlet with it is most lower
The water inlet of layer fin is connected, and cooling water is flowed by undermost fin, and the fin 19 is in continuous bending structure, structure
As shown in Figure 3.The end of adjacent upper layer and lower layer fin is connected, and cooling water outlet is connected with the water outlet of top layer's fin
Logical, cooling water enters from lowest level fin, is flowed out to one layer of fin topmost.Compression is provided on the kettle cover of two level cooling reactor
Air puff device, compressed air blowning installation are connected with compressed gas source, compressed air purging when discharging.Two level cools down
The kettle cover of kettle is equipped with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.The bottom of two level cooling reactor is arranged
There is outlet valve 9；A pipeline being connected with waste gas absorbing system is provided on the kettle cover of two level cooling reactor 8.
The waste gas absorbing system is made of two negative pressure water touries 10 and acid mist absorbing device 11, two negative pressure water
Tourie is in series or is connected in parallel.Pipeline is provided at the top of negative pressure water tourie and by pipeline and acid mist absorbing device
Air-introduced machine be connected.Acid mist after the absorption of two level water tourie occurs in acid mist absorbing device with the droplet of liquid caustic soda solution
It is discharged into air again after neutralization reaction, workshop cycle is given after the concentration that the acid solution of negative pressure water tourie reaches certain to be made
With.
It elaborates below to the detailed preparation process of the present invention by taking the gold tailings of certain mine factory as an example, through analyzing,
The following m/m% of chemical composition in gold tailings：
Specific production stage is as follows：
(1), it by one or both of hydrofluoric acid, fluosilicic acid, is mixed with one or both of nitric acid, hydrochloric acid,
Mix acid liquor is made, hydrofluoric acid, fluosilicic acid, nitric acid or hydrochloric acid are technical grade；Or using industrial by-product.As excellent
Choosing, the mass concentration or volumetric concentration of hydrofluoric acid are 1~10%, and the mass concentration or volumetric concentration of fluosilicic acid are 10~30%,
The mass concentration or volumetric concentration of nitric acid are 2~20%, and the mass concentration or volumetric concentration of hydrochloric acid are 10%~20%.
Gold tailings are worn into 200 mesh hereinafter, the magnetic separation in ore grinding：Magnetic separation uses three-level wet magnetic separation：Use low (magnetic
Field intensity is magnetic separator+jigging machine of 3000-5000 Gausses) -- in (magnetic field intensity is magnetic separator+jump of 5000-10000 Gausses
Eliminate machine) -- high (magnetic field intensity is magnetic separator+jigging machine of 10000-25000 Gausses).The magnetic separator of three-level field strength carries out magnetic separation
And gravity treatment, recycling iron powder and heavy metal are carried out to greatest extent；After slurry after magnetic separation is sent into concentrator precipitation, then with ceramics mistake
It is spare after filter dehydration；It is if it is the tail mud after cyaniding, after flotation, then spare after being dehydrated with ceramic filter.If in tailing
It is relatively high containing alundum (Al2O3), calcium oxide, magnesia, then it needs material first to carry out sour processing with concentrated hydrochloric acid, makes therein big
Partial alkaline-metal and alkaline-earth metal are removed in the form of villaumite, removing acid solution, spare after progress flotation removing feldspar, are floatingly selected
Feldspar powder can do ceramic raw material.
(2), mix acid liquor is put into reaction kettle, opens the waste gas absorption in the agitating device and reaction system of reaction kettle
Device slowly puts into gold tailings powder in reaction kettle.
(3) if, contain hydrofluoric acid in the mix acid liquor of input, since it and silicon dioxde reaction process are a heat releases
Process then needs to open 70~85 DEG C of cooling water valve maintaining reaction temperature outside reaction response kettle.If the mix acid liquor of input
In without containing hydrofluoric acid contain fluosilicic acid, then need to open the spiral four installed on the steam valve and kettle inner wall of reacting kettle jacketing
Heat source valve on the kettle outer wall of fluorine bundle of capillary tubes is slowly heated to reaction kettle.Hydrofluoric acid or fluosilicic acid in mix acid liquor and Huang
Silicon dioxde reaction in golden tailing generates silicon tetrafluoride gas, which is dissolved in formation fluorine silicon in the water of reaction system
Acid continues to dissolve a small amount of feldspar of the silica in gold tailings, until they are decomposed completely.The tetrafluoro that another part overflows
SiClx gas and the nitric acid/HCl gas and vapor of volatilization are brought by negative pressure in cooling reactor together.Hydrochloric acid in mixed acid
With nitric acid acid solution then with other metal reactions in material.Nitric acid primarily serves oxidation in this reaction process, it can be with
Sulfuric acid is oxidized to containing the element sulphur in golden troilite, sulphur copper mine, iron and copper oxidation generate iron oxide and copper oxide, to make
Gold, silver, lead, zinc etc. are therefrom separated in sulfide mineral；Hydrochloric acid plays complexing, and the metal after decomposition is then with the shape of ion
Formula enters in acid solution.
(4), control cooling reactor in cooling temperature be 10~40 DEG C, mixed gas react in cooling reactor generation HF,
Cl2/NO2、SiO2·nH2O, chemical equation are as follows：
SiF4+4HNO3+nH2O=4HF ↑+4NO2↑+SiO2·nH2O+O2↑
Wherein HF and Cl2/NO2It overflows from level-one cooling reactor and two level cooling reactor, is inhaled into waste gas absorbing system and by water
Midwifery can be followed at hydrofluoric acid, the hydrochloric acid/nitric acid for reuse, the hydrofluoric acid, hydrochloric acid/nitric acid after being concentrated to certain concentration
Ring uses；The problem of greatly having saved the cost and environmental protection treatment waste water in production in this way.
And SiO2·nH2O slowly condenses on the cooling disk being adsorbed in level-one cooling reactor, from beginning on cooling disk
Cohesion, then knot is in glittering and translucent spherical particle naturally at leisure, is flocked together as fish-egg, it is very beautiful, when level-one is cold
But when the cooling disk of kettle gathers a certain amount, opening of rotary shaft device, shaft drives cooling disc rotary, in the work of centrifugal force
Under, material is thrown to kettle wall, then the bottom of level-one cooling reactor is blown to compressed air, and the outlet valve through bottom is sent to drying
Process；After the material for having handled level-one cooling reactor, two level cooling reactor then directly opens compressed air valve, directly the object of condensation
The outlet valve through bottom is sent to drying process after material blows to bottom；
(5), it is in acidity since material contains moisture, and the volatilization of hydrofluoric acid, ocratation and nitric acid or HCl gas
Property is extremely strong, therefore before it is dried, first by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein
Remaining sour gas HF and Cl2/NO2, then it is dried again, can be prepared by gas-phase silica product after dry, in product
SiO2Content is more than 99.9%, and multiple spot BET method measurement the specific area is not less than 380m2/g。
(6), it after the completion of above-mentioned reaction, filtering while hot, filter residue is mainly aluminum trifluoride, after analyzing chemical composition therein,
The aluminum trifluoride product of high-purity can be obtained after purification again.Filtrate is sent into evaporator evaporation, the acid that when evaporation generates while hot
Fog gas carries out two level or more absorption with water tourie and becomes acid solution, after acid solution reaches a certain concentration, returns again to workshop weight
New to utilize, unabsorbed tail gas empties after being neutralized with acid fog absorption tower；After the acid solution in evaporator is evaporated, stop
Evaporation.It is washed with water except after the salt in solid residue, then it is handled with sulfuric acid, isolates copper sulphate, ferrous sulfate, sulphur
After sour zinc, then analyze it, according to analysis result, purification & isolation carried out to various metallic elements, you can obtain gold, silver,
Platinum, rhodium, lead and other more than 30 plant metallic element；Thus the valuable metal element in gold tailings can be efficiently returned
It receives, gold tailings resource is made to obtain science, reasonable and environmental-friendly, effective, maximumlly utilization.
Claims (1)
1. a kind of for preparing gas-phase silica as raw material using gold tailings and recycling the device in smithcraft, the technique packet
Include following steps:(1), it by fluorine-containing acid solution, is mixed with the mixed acid of hydrochloric acid with nitric acid or nitric acid, it is standby that mix acid liquor is made
With；Gold tailings are worn into 200 mesh of grain size hereinafter, the magnetic separation in ore grinding, with recycling iron powder and heavy metal；Slurry after magnetic separation is sent
It is spare that gold tailings powder is made after entering concentrator precipitation, then after being dehydrated with ceramic filter；
(2), mix acid liquor is put into reaction kettle, opens the waste gas absorption dress in the agitating device and reaction system of reaction kettle
It sets, gold tailings powder is put into reaction kettle；
(3), it is 70~85 DEG C to control the reaction temperature in reaction kettle, the hydrofluoric acid or fluosilicic acid in mix acid liquor and gold tailings
Silicon dioxde reaction in powder generates silicon tetrafluoride gas, the sour gas to be volatilized in the silicon tetrafluoride gas and mix acid liquor
And vapor is brought by negative pressure in cooling reactor together；
(4), it is 10~40 DEG C to control the cooling temperature in cooling reactor, and mixed gas is reacted in cooling reactor generates HF, NO2、
SiO2·nH2O, wherein HF and NO2Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generate for reuse hydrofluoric acid,
Nitric acid, SiO2·nH2O condensations are adsorbed on the cooling device in cooling reactor, collect the SiO in cooling reactor2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes wherein remaining sour gas
HF and NO2, it is then dried again, can be prepared by gas-phase silica product after dry, SiO in product2Content is more than 99.9%,
Its multiple spot BET method measurement the specific area is not less than 350m2/g；
(6), it is filtered after the completion of reaction in reaction kettle, aluminum trifluoride is can be obtained into filter residue after purification, filtrate is sent into and is evaporated
Device evaporates, and the acid mist gas gas that when evaporation generates, which with water tourie absorb, becomes acid solution, and it is again sharp again that acid solution returns to workshop
With unabsorbed tail gas empties after being neutralized with acid fog absorption tower；
After the acid solution in evaporator is evaporated, stop evaporation, is washed with water except after the salt in solid residue, then with sulfuric acid to solid
Residue is handled, after isolating sulfate, finally to its component analysis, according to analysis result, to various metallic elements into
Row purification & isolation recycles；
It is characterized in that：Described device includes that hot-air is sent into system, chemical reaction system, cooling system and waste gas absorption system
System, wherein hot-air are sent into system and are used for storing compressed air and are sent into chemical reaction system after being heated to air；Institute
Chemical reaction system is stated to be made of acid solution storage tank, feed bin and reaction kettle, the bottom of acid solution storage tank and feed bin by pipeline with react
Kettle is connected, and agitating device is provided in reaction kettle, the liner of reaction kettle is heatproof, acidproof, wear-resistant material, in reactor bottom
Top, be equipped with an annular pipe, be evenly distributed with air hole or permeability cell on pipe, be provided in reaction kettle one with
On the vertical tube that is connected of pipe with annular, the pipe valve on kettle cover that the top of the vertical tube passes through reaction kettle send with hot-air
Enter system to be connected；Kettle inner wall is equipped with tetrafluoro capillary that be close to kettle wall and helically linear from top to bottom or from bottom to top
The upper and lower ends of beam, the tube bank are connect with the cold and hot medium outside kettle wall by its valve respectively, by the capillary in tube bank
It is passed through cold and hot medium, provides and is heated or cooled for reaction system in kettle；
Cooling system is composed in series by level-one cooling reactor and two level cooling reactor；Wherein level-one cooling reactor is connected with reaction kettle, instead
The kettle cover of kettle is answered to be equipped with a pipeline for being connected with level-one cooling reactor and being deep into level-one cooling reactor bottom center, level-one cooling
Kettle is internally provided with cooling device, and the bottom of level-one cooling reactor is provided with outlet valve, is provided on the kettle cover of level-one cooling reactor
The inside of a piece pipeline for being connected with two level cooling reactor and being deep into two level cooling reactor bottom center, the two level cooling reactor is set
It is equipped with cooling device, the bottom of two level cooling reactor is provided with outlet valve；One and exhaust gas are provided on the kettle cover of two level cooling reactor
The pipeline that absorption system is connected, the waste gas absorbing system is by more than one negative pressure water tourie and acid mist absorbing device
It forms, pipeline is provided at the top of negative pressure water tourie and is connected with the air-introduced machine in acid mist absorbing device by pipeline；
Be evenly distributed on the pipe it is a diameter of 10~20mm's and towards different permeability cells, between adjacent permeability cell
Spacing be 50~150mm, and the angle between the stretching direction of adjacent permeability cell is 60~120 °, is provided in reaction kettle
Two vertical tubes, two vertical tubes are connected to the left and right ends of pipe.
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| 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 |
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