CN105197959B - Chemically floatation handles the method that fluorine resource is reclaimed in low product bauxite technique - Google Patents
Chemically floatation handles the method that fluorine resource is reclaimed in low product bauxite technique Download PDFInfo
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Abstract
The present invention provides a kind of chemically floatation and handles the method that fluorine resource is reclaimed in low product bauxite technique, comprises the following steps：It is that the low product bauxite ore particles of 50~100 purposes and hydrogen fluoride gas are placed in fluidized-bed reactor by granularity, reacts 10~30 min in room temperature~110 DEG C, obtain desiliconization solid residue and the gaseous products containing silicon fluoride；The gaseous products are absorbed using ethanol water, the hydrolysate containing silica is obtained；Ammoniacal liquor is added until pH value is 6~8 into the hydrolysate at 70~90 DEG C；Then it is aged 0.5~2 hour at 70~90 DEG C, obtains turbid solution；The turbid solution is filtered successively, the steps such as crystallization that are concentrated under reduced pressure reclaim ammonium fluoride solid.Above-mentioned recovery fluorine resource allocation method, which is mainly in the chemically waste gas decomposition of the low product bauxite of floatation processing, reclaims fluorine resource, turns waste into wealth, with the low advantage of environmental protection and energy saving, cost.
Description
Technical field
Technology is utilized the present invention relates to low product bauxite Decomposition-Synthesis, and in particular to a kind of chemically floatation handles low product
The method that fluorine resource is reclaimed in bauxite technique.
Background technology
With the fast continual development of national economy, the aluminum i ndustry of China also generates earth-shaking change.Aluminum i ndustry
Fast development preferably meet the development of the national economy and social development the need for, but consequently also bring resource and the energy is big
The problem of amount consumption.The particularly poor problem of bauxite resource, it has also become the bottleneck problem of restriction China aluminum i ndustry sustainable development.
According to statistics, between 2001~2007 years, China is used for aluminum oxide, the bauxite grade of aluminum fluoride production and is remarkably decreased, ore aluminium silicon
Than being dropped to averagely less than 7 from average by about 10, due to the operation of new alumina producer in 2008, the nervous office of resource is more exacerbated
Face, the average alumina silica ratio of ore is reduced to less than 6.
Only have HF to improve the alumina silica ratio of low product bauxite under normal temperature, so low product bauxite Decomposition-Synthesis utilizes technology
Need to decompose low product bauxite using fluorine-containing auxiliary agent, the fluorine of addition is partly into absorption system and directly reclaimed, a part
To exist in the form of villiaumite in potassium feldspar decomposition residue, fluorine mass content is about 7%~10%, if not reclaiming this part of fluorine,
They will enter after leaching loses in filtrate.Fluorine resource belongs to strategic reserves resource, and exploitation of the country to fluorine resource is real
Row quota restriction, this results in fluorine resource price costliness, so the fluorine resource in low product bauxite waste gas decomposition how is reclaimed, with
Just it is current urgent problem to be solved to recycle.
The content of the invention
In view of this, recovery fluorine resource in low product bauxite technique is handled it is necessory to provide a kind of chemically floatation
Method, to solve the above problems.
The method that the present invention provides recovery fluorine resource in a kind of low product bauxite technique of chemically floatation processing, including with
Lower step：
Chemical flotation removes silicon：It is that the low product bauxite ore particles of 50~100 purposes and hydrogen fluoride gas are placed in fluid bed by granularity
In reactor, 10~30 min are reacted in room temperature~110 DEG C, desiliconization solid residue and the gas generation containing silicon fluoride is obtained
Thing；
Gas absorbs ammonolysis：The gaseous products are absorbed using ethanol water, the hydrolysis containing silica is obtained
Product；Ammoniacal liquor is added until pH value is 6~8 into the hydrolysate at 70~90 DEG C；Then 70~90 DEG C be aged 0.5~
2 hours, obtain turbid solution；
Reclaim fluorine resource：The turbid solution is filtered, fluorine-containing filtrate is obtained；The fluorine-containing filtrate is evaporated under reduced pressure successively
Concentration, crystallization, drying process, obtain ammonium fluoride crystal.
Wherein, the alumina silica ratio in the low product bauxite is less than or equal to 7.With oxidation in the raw ore of the low product bauxite
Aluminium, silica are main component, and containing in the impurity, and the low product bauxite such as potassium oxide, titanium oxide, iron oxide
What each element substantially existed in the form of an oxide, aluminum oxide therein specifically can be divided mainly into diaspore, three water
Aluminium stone and boehmite.Therefore, " removal efficiency of silicon " and " desiliconization rate " herein each means the removal efficiency of silica,
" aluminium content " refers to alumina content, and " rate of recovery of aluminium " refers to the rate of recovery of aluminum oxide, and " silicone content " refers to containing for silica
Amount.Contain diaspore, part gibbsite and part boehmite in low product alum clay green ore.The temperature of the room temperature
For 10~40 DEG C.In addition, " hydrogen fluoride gas " specifically described herein refers to anhydrous hydrogen fluoride gas.
Based on above-mentioned, the step of chemical flotation removes silicon includes：It is first low product alum clay described in 50~100 purposes by granularity
Ore deposit particle is placed in the fluidized-bed reactor, then is passed through the hydrogen fluoride gas into the fluidized-bed reactor, in negative pressure
Under the conditions of, controlling reaction temperature is 20~40 DEG C, the hydrogen fluoride gas stops 10 in the fluidized-bed reactor~
20min, to remove element silicon and part ferro element in the low product bauxite ore particles, obtains the desiliconization solid residue.Its
In, the reaction equation that the step is related to is：
Fe2O3 + HF = FeF3 + 3H2O, SiO2 + 4HF = SiF4 + 2H2O。
Due to using hydrogen fluoride gas in desiliconization process as reactant, in order to prevent the fluidized-bed reactor by
Acid corrosion, the fluidized-bed reactor should be used as lining using polytetrafluoroethylene (PTFE).
Based on above-mentioned, in the chemical flotation removes silicon step, the vacuum of the negative pressure is 0.08~0.1 MPa.This
It is primarily due in desiliconization process, has the generation of silicon fluoride gas, so, decomposed in the low product bauxite ore particles
When, the fluidized-bed reactor is in negative pressure state.
Based on above-mentioned, the step of chemical flotation removes silicon also includes：With desiliconization solid residue described in clear water washing and filtering,
Obtain high product bauxite.
Based on above-mentioned, the temperature of the clear water is 80~90 DEG C.The desiliconization solid residue is cleaned with clear water and can utilized
The hydrogen fluoride wherein remained farthest removes the elements such as the partial-titanium, the iron that remain in the desiliconization solid residue, but also
It can reduce except the content of Fluorine in Ores element after element silicon.
Based on above-mentioned, the step of gas absorbs ammonolysis includes：By the gaseous products under -6~-4 kPa, lead to
Enter absorption tower to be absorbed and hydrolysis, using the ethanol water as absorbing liquid, ethanol in the absorbing liquid with
The volume ratio of water is 1:1 so that the gaseous products are hydrolyzed at 70~90 DEG C, generate the hydrolysis containing silica
Product；The hydrolysate is passed through ammonolysis kettle, ammoniacal liquor is added into the ammonolysis kettle and neutralizes the hydrolysate, and is made described
The pH of material in ammonolysis kettle is 6~8；After neutralization is finished, it is aged 0.5~2 hour at 70~90 DEG C, obtains the turbid solution.
Wherein, in the step of gas absorbs ammonolysis, the gaseous products mainly include silicon fluoride gas and fluorine
Change hydrogen, and silicon fluoride gas hydrolysis generation fluosilicic acid, fluosilicic acid ammonolysis generation ammonium fluoride；The reaction being related in the step
Principle is mainly：
3SiF4 + 2H2O = 2H2SiF6 + SiO2↓, HF+ NH3 = NH4F,
H2SiF6 + 6 NH3 + 2H2O = 6 NH4F + SiO2↓。
Include based on above-mentioned, the step of the recovery fluorine resource：It is placed on the dirty solution conveying in the ammonolysis kettle
Filtered into filter press, obtain the fluorine-containing filtrate and white carbon semi-finished product；Then, it is in vacuum at 70~90 DEG C first
The evaporation process that is concentrated under reduced pressure during 0.05~0.08 MPa to the fluorine-containing filtrate progress reaches 12 mol/L until being fluorinated ammonium concentration,
Then add ethanol solution and in 20~30 DEG C of crystallisation by cooling, be centrifugally separating to obtain the ammonium fluoride crystal.Wherein, in cooling knot
During the brilliant ammonium fluoride crystal, fluorine can be accelerated to add ethanol solution in 12 mol/L ammonium fluoride solution to concentration
Change the precipitation of ammonium crystal.
Specifically, the step of recovery fluorine resource includes：The dirty solution being placed in the ammonolysis kettle is transported to
Filtered in filter press, obtain the fluorine-containing filtrate and white carbon semi-finished product；By the fluorine-containing filtrate by being pumped into ammonium fluoride
In condensing crystallizing kettle, it is allowed at 70~90 DEG C, when vacuum is 0.05~0.08 MPa, in the ammonium fluoride condensing crystallizing kettle
Concentration, until the fluorination ammonium concentration in the ammonium fluoride condensing crystallizing kettle reaches 12 mol/L；Then concentrated to the ammonium fluoride
Ethanol solution is added in crystallization kettle and crystallisation by cooling is carried out at 20~30 DEG C using cooling water recirculation system；By the magma after crystallization
Separated through centrifuge, dry, obtain the ammonium fluoride crystal.
Also include based on above-mentioned, the step of the recovery fluorine resource：Washing, the dry white carbon semi-finished product prepare hard charcoal
It is black.
Based on above-mentioned, in the step of chemical flotation removes silicon, the low product bauxite ore particles are by successively to low
Product alum clay green ore is carried out obtained from broken, milled processed.
Compared with prior art, the chemically floatation that the present invention is provided, which is handled, reclaims fluorine resource in low product bauxite technique
Method be mainly using the low product bauxite of chemical flotation method processing during the gaseous products that produce as primary raw material,
By absorption, ammonolysis, filter, the steps such as crystallization that are concentrated under reduced pressure reclaim ammonium fluoride solid, improve the rate of recovery of fluorine, reduce
The consumption of fluorine so that fluorine resource can be recycled, and fluorine cyclic utilization rate can reach more than 90%, solve fluorine resource short
The problem of lacking, cost is reduced, environmental pollution is reduced, handling process is simple and easy to apply, effect is very good.Therefore, the present invention is carried
The method that the chemically floatation supplied handles recovery fluorine resource in low product bauxite technique makes full use of acid heat method to handle low product aluminium
Waste gas during native ore deposit, it is to avoid exhaust emission environment, turns waste into wealth, with the low advantage of environmental protection and energy saving, cost and important
Positive effect.In addition, during fluorine resource is reclaimed, the present invention is also prepared by washing, the dry white carbon semi-finished product
White carbon, so as to more fully utilize the waste gas decomposition of low product bauxite, turns waste into wealth.
Further, since the aluminium in bauxite almost exists in the form of diaspore, and diaspore is at low temperature
More stable, not with acid-base reaction, the soluble elements such as iron in ore can but use acid removing.Silica energy and hydrogen fluoride
Reaction, therefore, using low product bauxite ore particles and hydrogen fluoride gas abundant haptoreaction in a fluidized bed reactor, can be removed
Most element silicons and some acid soluble impurities in the low product bauxite ore particles, such as iron oxide, even more so that silicon
The extrusion rate of element reaches 98.84%, so as to improve the alumina silica ratio of low product bauxite, obtains the high product bauxite, and the Gao Pin
The alumina silica ratio of bauxite is more than 10, is conducive to making full use of for low product bauxite.
Brief description of the drawings
Fig. 1 is that the chemically floatation that the present invention is provided handles the method flow that fluorine resource is reclaimed in low product bauxite technique
Figure.
Fig. 2 is influence curve figure of the granularity to high product bauxite product component of low product bauxite ore particles.
Fig. 3 is that influence of the reaction temperature of low product bauxite ore particles and hydrogen fluoride gas to high product bauxite product component is bent
Line chart.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
Returned referring to Fig. 1, first embodiment of the invention is provided in a kind of low product bauxite technique of chemically floatation processing
The method for receiving fluorine resource, comprises the following steps：
Chemical flotation removes silicon：Low product alum clay green ore as shown in table 1 is provided, and it is placed in disintegrating machine broken
Broken, the low product bauxite after then crushing, which is placed in grinder, to be ground, and obtains granularity for the low product bauxite of 100 purposes
Grain；Take the low product bauxite ore particles 10.00g of 100 mesh to be placed in fluidized-bed reactor, hydrogen fluoride gas is passed through 110 DEG C
In the fluidized-bed reactor, 30min is reacted, desiliconization solid residue and the gaseous products containing silicon fluoride is obtained；Use clear water
Clean, filter the desiliconization solid residue, obtain the high product alum clay mineral products of 6.969 g.Known using X-ray fluorescence method analysis
Road：SiO in high product alum clay mineral products2Content is 0.18%, and the removal efficiency of silicon is 99.61%, and the content of fluorine element is 42.89%,
Al2O3Content is 52.33%.
The component of the low product alum clay green ore of table 1
| Component | Al2O3 | SiO2 | K2O | TiO2 | Fe2O3 | Other | Burning subtracts |
| Content/% | 46.14 | 32.42 | 2.48 | 3.21 | 2.72 | 1.31 | 11.70 |
Gas absorbs ammonolysis：By the gaseous products under -6 kPa, it is passed through absorption tower and is absorbed and hydrolysis,
Using the ethanol water as absorbing liquid, the volume ratio of ethanol and water therein is 1:1 so that the gaseous products exist
Hydrolyzed at 70 DEG C, generate the hydrolysate containing silica；The hydrolysate is passed through ammonolysis kettle, to the ammonolysis
Ammoniacal liquor is added in kettle and neutralizes the hydrolysate, and makes the pH of the material in the ammonolysis kettle be 6；After neutralization is finished, at 70 DEG C
Ageing 1 hour, obtains the turbid solution.
Reclaim fluorine resource：The dirty solution being placed in the ammonolysis kettle is transported in filter press and filtered, and obtains fluorine-containing
Filtrate and white carbon semi-finished product；By fluorine-containing filtrate by being pumped into ammonium fluoride condensing crystallizing kettle, it is allowed in 70 DEG C, vacuum
During for 0.05~0.06 MPa, concentrated in the ammonium fluoride condensing crystallizing kettle, until in the ammonium fluoride condensing crystallizing kettle
Fluorination ammonium concentration reaches 12mol/L；Then ethanol solution is added into the ammonium fluoride condensing crystallizing kettle and is followed using cooling water
Loop system carries out crystallisation by cooling at 20 DEG C；Magma after crystallization is separated through centrifuge, dried, the ammonium fluoride is obtained brilliant
Body, the rate of recovery of ammonium fluoride is 85%.The white carbon semi-finished product are washed, drying process, obtain white carbon finished product.
Embodiment 2
Second embodiment of the invention provides the technique that a kind of use chemical flotation method removes silicon from low product bauxite, and it is with the
The difference of one embodiment is：
In the chemical flotation removes silicon step, the reaction temperature of the low product bauxite ore particles and hydrogen fluoride gas is 70
DEG C, 15 min of reaction obtain the high product alum clay mineral products of 5.400 g.Known using X-ray fluorescence method analysis：High product bauxite
SiO in product2Content is 1.41%, and the removal efficiency of silicon is 97.65%, and the content of fluorine element is 23.41%, Al2O3Content is
68.53%。
In the step of gas absorbs ammonolysis, the gaseous products are passed into absorption tower under -4 kPa, institute
State gaseous products to hydrolyze at 80 DEG C, the pH of the material after ammonolysis is neutralized in ammonolysis kettle is 8, and is aged 1.5 hours at 80 DEG C.
It is described recovery fluorine resource the step of in, the fluorine-containing filtrate be 80 DEG C, vacuum be 0.06~0.07 MPa
What Shi Jinhang was concentrated under reduced pressure；Crystallisation by cooling is carried out at 30 DEG C；The rate of recovery of final ammonium fluoride is 88.2%.
Embodiment 3
Third embodiment of the invention provides the technique that a kind of use chemical flotation method removes silicon from low product bauxite, and it is with the
The difference of one embodiment is：
In the chemical flotation removes silicon step, the reaction temperature of the low product bauxite ore particles and hydrogen fluoride gas is 20
DEG C, reaction 20min obtains the high product alum clay mineral products of 5.410 g.Known using X-ray fluorescence method analysis：High product bauxite
SiO in product2Content is 5.19%, and the removal efficiency of silicon is 91.33%, and the content of fluorine element is 19.80%, Al2O3Content is
65.20%。
In the step of gas absorbs ammonolysis, the gaseous products are passed into absorption tower under -5 kPa, institute
State gaseous products to hydrolyze at 78 DEG C, the pH of the material after ammonolysis is neutralized in ammonolysis kettle is 8, and is aged 2 hours at 78 DEG C.
It is described recovery fluorine resource the step of in, the fluorine-containing filtrate be 78 DEG C, vacuum be 0.06~0.07 MPa
What Shi Jinhang was concentrated under reduced pressure；Crystallisation by cooling is carried out at 28 DEG C；The rate of recovery of final ammonium fluoride is 89%.
Embodiment 4
Fourth embodiment of the invention provides the technique that a kind of use chemical flotation method removes silicon from low product bauxite, and it is with the
The difference of one embodiment is：
In the chemical flotation removes silicon step, the granularities of the low product bauxite ore particles is 50 mesh, itself and fluorination hydrogen
The reaction temperature of body is 30 DEG C, and reaction 20min obtains the high product alum clay mineral products of 5.350 g.Analyzed using X-ray fluorescence method
Know：SiO in high product alum clay mineral products2Content is 9.89%, and the removal efficiency of silicon is 83.68%, and the content of fluorine element is 14.81%,
Al2O3Content is 64.97%.
In the step of gas absorbs ammonolysis, the gaseous products are passed into absorption tower under -4 kPa, institute
State gaseous products to hydrolyze at 75 DEG C, the pH of the material after ammonolysis is neutralized in ammonolysis kettle is 7, and is aged 1.5 hours at 75 DEG C.
It is described recovery fluorine resource the step of in, the fluorine-containing filtrate be 75 DEG C, vacuum be 0.06~0.07 MPa
What Shi Jinhang was concentrated under reduced pressure；Crystallisation by cooling is carried out at 23 DEG C；The rate of recovery of final ammonium fluoride is 90.2%.
Embodiment 5
Fifth embodiment of the invention provides the technique that a kind of use chemical flotation method removes silicon from low product bauxite, and it is with the
The difference of one embodiment is：
In the chemical flotation removes silicon step, the granularities of the low product bauxite ore particles is 200 mesh, itself and fluorination hydrogen
The reaction temperature of body is 40 DEG C, and reaction 10min obtains the high product alum clay mineral products of 5.343 g.Analyzed using X-ray fluorescence method
Know：SiO in high product alum clay mineral products2Content is 4.90%, and the removal efficiency of silicon is 92.34%, and the content of fluorine element is 20.15%,
Al2O3Content is 65.45%.
In the step of gas absorbs ammonolysis, the gaseous products are passed into absorption tower under -5 kPa, institute
State gaseous products to hydrolyze at 70 DEG C, the pH of the material after ammonolysis is neutralized in ammonolysis kettle is 7, and is aged 1.5 hours at 70 DEG C.
It is described recovery fluorine resource the step of in, the fluorine-containing filtrate be 70 DEG C, vacuum be 0.06~0.07 MPa
What Shi Jinhang was concentrated under reduced pressure；Crystallisation by cooling is carried out at 25 DEG C；The rate of recovery of final ammonium fluoride is 91.2%.
It has been investigated that, in the low product bauxite ore particles and the hydrogen fluoride gas course of reaction, the low product alum clay
The factors such as the granularity and reaction temperature of ore deposit particle have an impact to desiliconization effect, so as to influence the rate of recovery of fluorine resource.Alumina silica ratio is
Examine whether reaction reaches the important indicator of requirement, should be as much as possible in order to reduce the consumption that bauxite formality handles raw material
Remove element silicon.But, it is necessary to use hydrogen fluoride gas in the technical process of desiliconization, but a certain amount of fluorine element can be introduced,
So the content of fluorine element is also to judge the whether rational important evidence of this method.Therefore, below will be described low by testing
The granularity and reaction temperature of product bauxite ore particles are to the content of the aluminium content in high product alum clay mineral products, silicone content and fluorine element
Influence.
1. influence of the granularity of low product bauxite ore particles to high product bauxite product component
Ore grain size is probed into using experiment of single factor, experiment condition is：The low product alum clay of component shown in above-mentioned table 1
The g of green ore 10.00, reaction temperature normal temperature, hydrogen fluoride is passed through the h of time 1, then seals 30 min, is washed with clear water, dries.
Obtained experimental data is as shown in table 2 below and Fig. 2：
Influence of the low product bauxite ore particles granularity of table 2 to high product bauxite product component
| Sequence number | Low product bauxite ore particles granularity/mesh | Product quality/g | Aluminium element content/% in product | Silicon content/% in product | Fluorine element content/% in product | Desiliconization rate/% |
| 1 | 50 | 5.350 | 64.972 | 9.888 | 14.807 | 83.68 |
| 2 | 100 | 5.410 | 65.201 | 5.193 | 19.797 | 91.33 |
| 3 | 200 | 5.343 | 65.452 | 4.896 | 20.147 | 92.34 |
It can be seen that from table 2 and Fig. 2：With the reduction of the low product bauxite ore particles granularity, the extrusion rate of element silicon
Gradually increase, and aluminium content is basically unchanged, the alumina silica ratio of the high product alum clay mineral products obtained after reaction has met follow-up alkali soluble
Condition, most important is exactly the introduction amount for controlling fluorine element, and the content of fluorine element is with the low product bauxite ore particles granularity
Reduce and increase.Therefore, the granularity of the low product bauxite ore particles is finally selected in 50~100 mesh.
2. influence of the reaction temperature to high product bauxite product component
Experiment carries out single factor analysis to temperature conditionss.Experiment condition is：The low g of product bauxite ore particles 10.00 of 100 purposes,
At a temperature of differential responses, control hydrogen fluoride gas to be passed through the time for 1 h, then seal 30min, be washed with water, dry.Obtain
Experimental data table 3 and Fig. 3 shown in：
Influence of the reaction temperature of table 3 to high product bauxite product component
| Sequence number | Reaction temperature/DEG C | Product quality/g | Content/% of aluminium element in product | Content/% of element silicon in product | Content/% of fluorine element in product | Desiliconization rate/% |
| 1 | 110 | 6.969 | 52.327 | 0.180 | 42.885 | 99.61 |
| 2 | 90 | 6.365 | 64.105 | 0.438 | 30.014 | 99.14 |
| 3 | 70 | 5.400 | 68.524 | 1.411 | 23.413 | 97.65 |
| 4 | 50 | 5.337 | 67.382 | 3.261 | 21.735 | 94.63 |
| 5 | Normal temperature | 5.410 | 65.201 | 5.193 | 19.797 | 91.33 |
As can be seen from Table 3：With the increase of reaction temperature, the quality of the high product alum clay mineral products obtained after reaction
Increase, reason is the increase with reaction temperature, and some of aluminium elements participate in reaction, have introduced fluorine element, have caused most
The increase of finished product quality.In addition, as can be seen from Figure 3：With the increase of reaction temperature, the extrusion rate of element silicon gradually increases
Plus, and aluminium content has fraction of reduction, it may be possible to because caused by Oil repellent increase, the rate of recovery of aluminium maintains essentially in 86%
The alumina silica ratio reacted under left and right, normal temperature has reached 13, meets alkali soluble condition, and the introduction amount of fluorine element is seldom.Therefore, most
Good reaction temperature is 20~40 DEG C of normal temperature.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
The embodiment of the present invention can be modified or equivalent substitution is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical scheme, it all should cover among claimed technical scheme scope of the invention.
Claims (7)
1. a kind of chemically floatation handles the method that fluorine resource is reclaimed in low product bauxite technique, comprise the following steps：
Chemical flotation removes silicon：It is first that the low product bauxite ore particles of 50~100 purposes are placed in fluidized-bed reactor by granularity, then to institute
State and hydrogen fluoride gas is passed through in fluidized-bed reactor, in the case where vacuum is 0.08~0.1MPa condition of negative pressure, controlling reaction temperature
For 20~40 DEG C, the hydrogen fluoride gas stops 10~20 min in the fluidized-bed reactor, to remove the low product aluminium
Element silicon and part ferro element in native ore deposit particle, obtain desiliconization solid residue and the gaseous products containing silicon fluoride；
Gas absorbs ammonolysis：The gaseous products are absorbed using ethanol water, the hydrolysate containing silica is obtained；
Ammoniacal liquor is added until pH value is 6~8 into the hydrolysate at 70~90 DEG C；Then it is small in 70~90 DEG C of ageings 0.5~2
When, obtain turbid solution；
Reclaim fluorine resource：The turbid solution is filtered, fluorine-containing filtrate is obtained；Carry out reduction vaporization successively to the fluorine-containing filtrate dense
Contracting, crystallization, drying process, obtain ammonium fluoride crystal.
2. the method according to claim 1 for reclaiming fluorine resource, it is characterised in that the step of chemical flotation removes silicon is also
Including：With desiliconization solid residue described in clear water washing and filtering, high product bauxite is obtained.
3. the method according to claim 2 for reclaiming fluorine resource, it is characterised in that the step of the chemical flotation removes silicon
In, the temperature of the clear water is 80~90 DEG C.
4. the method according to claim 1 for reclaiming fluorine resource, it is characterised in that the step of gas absorbs ammonolysis is wrapped
Include：By the gaseous products under -6~-4 kPa, it is passed through absorption tower and is absorbed and hydrolysis, using the ethanol water
Solution is as absorbing liquid, and the volume ratio of ethanol and water in the absorbing liquid is 1:1 so that the gaseous products are 70~90
Hydrolyzed at DEG C, generate the hydrolysate containing silica；The hydrolysate is passed through ammonolysis kettle, to the ammonolysis kettle
Middle addition ammoniacal liquor neutralizes the hydrolysate, and makes the pH of the material in the ammonolysis kettle be 6~8；After neutralization is finished, 70~
90 DEG C are aged 0.5~2 hour, obtain the turbid solution.
5. the method according to claim 4 for reclaiming fluorine resource, it is characterised in that wrap the step of the recovery fluorine resource
Include：The dirty solution being placed in the ammonolysis kettle is transported in filter press and filtered, and obtains the fluorine-containing filtrate and white carbon
Semi-finished product；Then, it is dense to the fluorine-containing filtrate progress decompression when vacuum is 0.05~0.08 MPa first at 70~90 DEG C
Contracting evaporation process reaches 12mol/L until being fluorinated ammonium concentration, then adds ethanol solution and in 20~30 DEG C of crystallisation by cooling, centrifugation
The isolated ammonium fluoride crystal.
6. the method according to claim 4 for reclaiming fluorine resource, it is characterised in that also wrap the step of the recovery fluorine resource
Include：Washing, the dry white carbon semi-finished product prepare white carbon.
7. the method according to claim 1 for reclaiming fluorine resource, it is characterised in that the step of the chemical flotation removes silicon
In, the low product bauxite ore particles are by obtained from, milled processed broken to the progress of low product alum clay green ore successively.
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| CN103539157B (en) * | 2013-10-31 | 2016-06-01 | 洛阳氟钾科技股份有限公司 | The technique of fluorine resource is reclaimed from potassium feldspar decomposition residue |
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