CN105329974A - Method for recycling fluorine from fluorine-containing waste water - Google Patents
Method for recycling fluorine from fluorine-containing waste water Download PDFInfo
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- CN105329974A CN105329974A CN201510753562.8A CN201510753562A CN105329974A CN 105329974 A CN105329974 A CN 105329974A CN 201510753562 A CN201510753562 A CN 201510753562A CN 105329974 A CN105329974 A CN 105329974A
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Abstract
The invention relates to a method for recycling fluorine from fluorine-containing waste water and belongs to the field of environmental engineering water treatment. The method for recycling fluorine is achieved by adding self-made porous tobermorite to the fluorine-containing waste water, on one hand, Ca<2><+> dissolved out of the porous tobermorite and dissociative F<-> in the waste water can be subjected to a complex reaction, and indissolvable CaF<2> is formed; on the other hand, OH<-> dissolved out of the porous tobermorite can raise the pH value of the waste water, hydrolysis of HF in the waste water is promoted, the whole fluorine recycling process is maintained under the condition that the pH value ranges from 6.5 to 7.5, the pH value is not needed to be adjusted, thereby the whole fluorine recycling process is conducted spontaneously under the condition that the pH value is neutral, no extra chemical agent is needed to be added, the fluorine content in a recycled product is high, impurities such as heavy metal are not contained, and the recycled product can be utilized directly as a fluorine-containing product.
Description
Technical field
The present invention relates to a kind of method reclaiming fluorine, be specifically related to one and fluoride waste is processed, and utilize porous hydrated calcium silicate to carry out the method for efficient recovery to the fluorine in waste water, belong to environmental engineering water treatment field.
Background technology
Fluorine and fluorochemicals are with a wide range of applications in the industrial or agricultural such as plating, smelting, chemical industry, thermal power generation, but being emitted on of waste water containing fluorine result in soil to a great extent, the fluorine content of underground water increases.Long-term drinking fluorion (F
-) water that exceeds standard can cause the fluorosis such as dental fluorosis, skeletal fluorosis disease; On the other hand, as a kind of resource, fluorite resource is day by day in short supply.Therefore, from fluorine-containing trade effluent, reclaim fluorine, not only can reduce fluorine in water and to exceed standard the harm that HUMAN HEALTH is caused, also can promote the sustainable recycle of fluorine resource.
At present, the treatment process of high-concentration fluorine-containing waste water mainly contains coagulant sedimentation, absorption method, ion exchange method, induced crystallization method, electricity flocculation and electroosmose process, membrane technique etc.The moisture percentage in sewage sludge that precipitation process of coagulation produces is higher, and in product, the net content of fluorine is lower, is difficult to directly as fluorine-containing product recycle.Absorption method and ion exchange method can effectively be removed and reclaim fluorine, but still there is the problems such as higher, the follow-up desorption process of sorbing material preparation cost is more complicated, cause the cost recovery of fluorine to increase.Induced crystallization method reclaims fluorine by forming the fluorine-containing crystal such as Calcium Fluoride (Fluorspan), sodium aluminum fluoride, Sodium Silicofluoride, and reclaiming product can directly be used as fluorine-containing mineral; But, the higher fluorine-containing mineral of purity be obtained, need the crystallization nucleation process nucleating condition comparatively accurate with work that experience is longer.Electricity flocculates and the method such as electroosmose process, membrane technique ubiquity energy consumption is higher, water outlet pH value needs the problems such as adjustment further.Therefore, the efficient and economic method reclaiming fluorine from fluoride waste is developed day by day urgent.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of method of the recovery fluorine based on porous hydrated calcium silicate, described method is easy and simple to handle, and the content reclaiming fluorine in product is higher, can directly be used as fluorine-containing product.
The main component of industry fluoride waste is hydrofluoric acid (HF), and the pH value of actual fluoride waste is generally between 2.5-6.5.F in waste water
-come from the hydrolysis of HF, increase the hydrolysis that pH value is conducive to HF.Calcium Fluoride (Fluorspan) (CaF
2) best formation condition be pH=6.5-7.5.Porous hydrated calcium silicate can spontaneous stripping Ca in fluoride waste
2+and OH
-.The OH of porous hydrated calcium silicate stripping
-the pH value of waste water can be improved, promote HF hydrolysis, and under making whole fluorine removal process maintain the condition of pH=6.5-7.5, without the need to adjust ph.Porous hydrated calcium silicate stripping Ca
2+can with free F in waste water
-there is complex reaction, form the CaF of indissoluble
2.In addition, containing the more weak Ca-OH key of a large amount of bond energy in porous hydrated calcium silicate, Ca-OH easily and F
-there is ion-exchange.
The porous hydrated calcium silicate that the present invention is applied to, is prepared by following methods: with CaO and SiO
2respectively as calcareous and siliceous raw material, be 2.0 ~ 3.0 to prepare burden according to calcium, silicon mol ratio, the ratio being 30:1 according to the mass ratio of water and solid phase makes slurry, puts into reactor, with the ramp to 170 DEG C of 2 DEG C/min under 250r/min after strong stirring 30min; Then under 90r/min, be incubated 4.5h carry out Hydrothermal Synthesis.Naturally cool to room temperature after having reacted, filter slurry, dry at 105 DEG C, namely obtain porous hydrated calcium silicate, described porous hydrated calcium silicate degree of crystallinity is 14 ~ 16%, specific surface area is 100 ~ 150m
2/ g.
A kind of method reclaiming fluorine from fluoride waste of the present invention comprises following operative step:
(1) adjustment makes the initial mass concentration of fluorine in fluoride waste be 100 ~ 1000mg/L, and initial pH value is 5.5 ~ 6.0;
(2) in above-mentioned fluoride waste, add porous hydrated calcium silicate, add-on is 1 ~ 7g/L, mechanic whirl-nett reaction 30-60 minute under room temperature, and described room temperature is 20 ± 2 DEG C, and stirring intensity is 200 ~ 400rpm;
(3) in the reaction process of step (2), by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, F is used
-choice electrode detects F in solution
-mass concentration, work as F
-mass concentration no longer change and be reaction and complete;
(4) after above-mentioned reaction completes, mixed solution step (3) obtained leaves standstill, and time of repose is no more than 5 minutes, observes sedimental volume change, stops sedimentation when the volume of sediment no longer increases, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Wherein, whole fluorine removal process is without the need to additional calcium salt, and pH value is constant between 6.5 ~ 7.5 and without the need to additional adjustment.
Wherein, the difference of the quality before and after the settling drying that obtains of step (4) is the water ratio that fluorine reclaims product.
Wherein, in described fluorine recovery product, the mass concentration of fluorine is calculated by formula (1):
In formula: q
ethe mass concentration that fluorine reclaims fluorine in product, unit mg/g; C
0for F initial in fluoride waste
-mass concentration, unit mg/L; C
efor F when the reaction described in step (3) completes
-mass concentration, unit mg/L; V is the volume of fluoride waste, unit L; M is the quality that fluorine reclaims product, unit g.
In addition, X-ray diffractometer (XRD) fluorine analysis can be used to reclaim the dominant phase of product, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product.
Preferably, described porous hydrated calcium silicate, is prepare under the lower hydrothermal temperature of 110-170 DEG C, its calcium silicon mol ratio is 2.0 ~ 3.0, degree of crystallinity is 14 ~ 16%, specific surface area is 100 ~ 150m
2/ g.
Preferably, the mass concentration that fluorine reclaims fluorine in product is 60 ~ 70mg/g, and water ratio is below 8%, and the main component that fluorine reclaims product is Calcium Fluoride (Fluorspan) and calcium silicofluoride.
Beneficial effect:
(1) raw materials of porous hydrated calcium silicate is cheap and easy to get, and preparation process is simple, and preparation cost is lower, is easy to industry's enlarging production.
(2) fluorine removal process is spontaneous under the condition that pH value is neutral carries out, without the need to additional chemical agent.
(3) content reclaiming fluorine in product is higher, and not containing impurity such as heavy metals, can directly be used as fluorine-containing product.
Accompanying drawing explanation
Fig. 1 is in the embodiment of the present invention (1), and fluorine reclaims the FE-SEM figure of product appearance structure;
Fig. 2 is in the embodiment of the present invention (1), and fluorine reclaims the XRD figure of product dominant phase.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, carry out clear, complete description to the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The porous hydrated calcium silicate that the present invention is applied to, is prepared by following methods: with CaO and SiO
2respectively as calcareous and siliceous raw material, be 2.0-3.0 to prepare burden according to calcium, silicon mol ratio, the ratio being 30:1 according to the mass ratio of water and solid phase makes slurry, puts into reactor, with the ramp to 170 DEG C of 2 DEG C/min under 250r/min after strong stirring 30min; Then under 90r/min, be incubated 4.5h carry out Hydrothermal Synthesis.Naturally cool to room temperature after having reacted, filter slurry, dry at 105 DEG C, namely obtain porous hydrated calcium silicate, described porous hydrated calcium silicate degree of crystallinity is 14 ~ 16%, specific surface area is 100 ~ 150m
2/ g.
Real-Time Monitoring water-quality guideline of the present invention, water-quality guideline comprises: F
-mass concentration and pH value.
F in solution
-mass concentration F
-choice electrode detects; PH value pH electrode measures.
After measured, use water outlet pH=6.5 ~ 7.5 after the method for the invention process, the mass concentration that fluorine reclaims fluorine in product is 60 ~ 70mg/g, and it is 5 ~ 8% that fluorine reclaims product water ratio.
Embodiment 1:
In fluoride waste, the initial mass concentration of fluorine is 500mg/L, and initial pH value is 6.0.
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and mechanic whirl-nett reaction 30 minutes under room temperature, stirring intensity is 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 64.83mg/g, the water ratio that fluorine reclaims product is 5%, reclaims the exterior appearance of product as shown in Figure 1, and the main component that fluorine reclaims product is Calcium Fluoride (Fluorspan) and calcium silicofluoride, as shown in Figure 2.The settling time of solid matter is 5 minutes.
Embodiment 2:
In fluoride waste, the initial mass concentration of fluorine is 600mg/L, and the initial pH value of fluoride waste is 6.0
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and under room temperature, mechanic whirl-nett reaction 30 minutes stirring intensities are 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 65.17mg/g, the water ratio that fluorine reclaims product is 6%.The settling time of solid matter is 5 minutes.
Embodiment 3:
In fluoride waste, the initial mass concentration of fluorine is 700mg/L, and initial pH value is 6.0.
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and under room temperature, mechanic whirl-nett reaction 30 minutes stirring intensities are 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 65.33mg/g, the water ratio that fluorine reclaims product is 7%.The settling time of solid matter is 5 minutes.
Embodiment 4:
In fluoride waste, the initial mass concentration of fluorine is 800mg/L, and initial pH value is 6.0.
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and under room temperature, mechanic whirl-nett reaction 30 minutes stirring intensities are 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 65.67mg/g, the water ratio that fluorine reclaims product is 6%.The settling time of solid matter is 5 minutes.
Embodiment 5:
In fluoride waste, the initial mass concentration of fluorine is 900mg/L, and initial pH value is 6.0.
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and under room temperature, mechanic whirl-nett reaction 30 minutes stirring intensities are 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 65.67mg/g, the water ratio that fluorine reclaims product is 6%.The settling time of solid matter is 5 minutes.
Embodiment 6:
In fluoride waste, the initial mass concentration of fluorine is 100mg/L, and initial pH value is 6.0.
In above-mentioned fluoride waste, add porous hydrated calcium silicate, described porous hydrated calcium silicate add-on is 6g/L, and under room temperature, mechanic whirl-nett reaction 30 minutes stirring intensities are 300rpm.
In above-mentioned reaction process, by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, use F
-choice electrode detects F in solution
-mass concentration.
After above-mentioned reaction completes, mixed solution is left standstill, observe when sedimental volume no longer increases and stop sedimentation, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
Reclaim the dominant phase of product by X-ray diffractometer (XRD) fluorine analysis, observe by field emission electron scanning electron microscope (FE-SEM) exterior appearance that fluorine reclaims product; The mass concentration reclaiming fluorine in product is calculated with formula (1).
Experimental result: the mass concentration that fluorine reclaims fluorine in product is 65.83mg/g, the water ratio that fluorine reclaims product is 8%.The settling time of solid matter is 5 minutes.
Claims (5)
1. from fluoride waste, reclaim a method for fluorine, comprise following operative step:
(1) adjustment makes the initial mass concentration of fluorine in fluoride waste be 100 ~ 1000mg/L, and initial pH value is 5.5 ~ 6.0;
(2) in above-mentioned fluoride waste, add porous hydrated calcium silicate, add-on is 1 ~ 7g/L, mechanic whirl-nett reaction 30-60 minute under room temperature, and described room temperature is 20 ± 2 DEG C, and stirring intensity is 200 ~ 400rpm;
(3) in the reaction process of step (2), by the changing conditions of pH value in pH electrode Real-Time Monitoring reaction process, F is used
-choice electrode detects F in solution
-mass concentration, work as F
-mass concentration no longer change and be reaction and complete;
(4) after above-mentioned reaction completes, mixed solution step (3) obtained leaves standstill, and time of repose is no more than 5 minutes, observes sedimental volume change, stops sedimentation when the volume of sediment no longer increases, the record settling time; Utilize centrifugation to filter, described mixed solution is filtered the settling obtaining particulate form, then settling is dried 2h at 105 DEG C, namely obtain fluorine and reclaim product.
2. a kind of method reclaiming fluorine from fluoride waste as claimed in claim 1, is characterized in that the add-on of described porous hydrated calcium silicate is 6g/L.
3. a kind of method reclaiming fluorine from fluoride waste as claimed in claim 1 or 2, is characterized in that described fluorine removal process is without the need to additional calcium salt, and pH value is constant between 6.5 ~ 7.5 and without the need to additional adjustment.
4. a kind of method reclaiming fluorine from fluoride waste as claimed in claim 1 or 2, it is characterized in that described porous hydrated calcium silicate, be prepare under the hydrothermal temperature of 170 DEG C, its calcium silicon mol ratio is 2.0 ~ 3.0, degree of crystallinity is 14 ~ 16%, specific surface area is 100 ~ 150m
2/ g.
5. a kind of method reclaiming fluorine from fluoride waste as claimed in claim 1 or 2, it is characterized in that the mass concentration that described fluorine reclaims fluorine in product is 60 ~ 70mg/g, water ratio is below 8%, and the main component that fluorine reclaims product is Calcium Fluoride (Fluorspan) and calcium silicofluoride.
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Cited By (2)
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| CN105664842A (en) * | 2016-04-07 | 2016-06-15 | 景德镇陶瓷学院 | Calcium-based adsorbent for defluorination and application thereof |
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