CN107540041A - Application of the discarded concrete in removing fluorine from water - Google Patents
Application of the discarded concrete in removing fluorine from water Download PDFInfo
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- CN107540041A CN107540041A CN201710868824.4A CN201710868824A CN107540041A CN 107540041 A CN107540041 A CN 107540041A CN 201710868824 A CN201710868824 A CN 201710868824A CN 107540041 A CN107540041 A CN 107540041A
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- discarded concrete
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- 239000011737 fluorine Substances 0.000 title claims abstract description 91
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000004567 concrete Substances 0.000 title claims abstract description 45
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000002699 waste material Substances 0.000 claims abstract description 34
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- 239000004568 cement Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 238000006115 defluorination reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 238000005345 coagulation Methods 0.000 abstract description 4
- 230000015271 coagulation Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000013043 chemical agent Substances 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
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- 238000010183 spectrum analysis Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010028309 Muscle haemorrhage Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 230000001960 triggered effect Effects 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses application of the discarded concrete in removing fluorine from water, method is during application：（1）Using discarded concrete as raw material, after just broken, calcining, Behavior of Hardened Cement Paste is filtered out, will carry out selecting powder to separate after the Behavior of Hardened Cement Paste ball milling, particle of the collection cut size below 80 μm, obtain removing fluorine from water agent；（2）By step（1）In obtained removing fluorine from water agent input fluoride waste fluorine removal can be carried out to waste water.The applications expanding of discarded this building castoff of coagulation to fluoride waste is administered field by the present invention, prepare a kind of water body fluoride removal material, its reaction speed during removing fluorine from water is fast, in the absence of limit doped amount, utilization ratio is high, defluorination effect is stable, it can at room temperature operate, improve the resource utilization efficiency of waste water mudstone, also the high value added utilization for petrifying water mudstone in discarded concrete provides a Technology Ways.
Description
Technical field
The invention belongs to utilization of waste as resource field, and in particular to application of the discarded concrete in removing fluorine from water.
Background technology
Substantial amounts of building waste can be produced in the construction industry activity such as the construction of building or structures, finishing, removal, and
With the quickening quickly propelled with urbanization speed of China's infrastructure, building waste yield continues to increase.City according to statistics
It is building waste that 1/3 is there are about in city's rubbish；To its storage of the end of the year 2011 more than 2,000,000,000 tons, and newly-increased building waste exceedes every year
300000000 tons.Because the factory addressing of building waste landfill is improper in most cities or interim stacking, the big of land resource is not only caused
Amount wastes, and there is also great potential safety hazard.Meanwhile building waste during accumulation and landfill with the aqueous phase in surrounding environment
Interaction, its percolate can cause the pollution of surface water or underground water.
Discarded concrete is the important component of building waste, accounts for the 34% of building waste total amount.And China is discarded mixed
Solidifying soil resource utilization rate is but less than 5%.Recycling approach main at present is preparation Aggregate of recycled concrete, but again
Raw aggregate surface often adheres to a large amount of petrifying water mudstones, due to its higher porosity and water absorption rate and relatively low intensity, makes
Regeneration aggregate mechanical properties decrease is obtained, regeneration concrete workability is deteriorated, and volume stability deteriorates after hardening.So discarded coagulation
A large amount of petrifying water mudstones, which turn into, in soil restricts the principal element that discarded concrete prepares regeneration aggregate.
The relative shortage of research of utilization of petrifying water mudstone in discarded concrete, only research are collected mostly at present
In prepare building material field, such as prepare building block or again calcining prepare cement etc..But due to waste water mudstone hole
Gap rate is big, marks the building material product that thick water requirement is high, activity index is low, limit doped amount in use all be present, is prepared with it
Workability and mechanical property are poor.Simultaneously as the gelled matrix separated from discarded concrete contains a certain amount of inertia
Silica, this is also next difficult to the burning zone of cement raw grinding and clinker, makes the increase of f-CaO contents, clinker matter in clinker
Amount declines, and production cost improves.
Fluorine is to maintain one of necessary trace element of human normal vital movement, while is also the important raw material of industry, its
Had a wide range of applications in fields such as chemical fertilizer, metallurgy, space flight, refrigeration, organic synthesis, integrated circuit, glass.In above-mentioned application
Inevitably produce waste water containing fluorine, if processing be not good at not only can generation environment pollution, finally can also threaten the mankind
Health.For example, a small amount of fluorine（Within 150mg）With regard to a series of slight illness can be triggered, more fluorine-containing chemical combination is taken in human body
Thing can then cause acute poisoning.Because intake is different, various illnesss can be produced, such as apocleisis, nausea, stomachache, gastric ulcer, take out
Muscle bleeding is even dead.
The processing common method on fluoride waste includes chemical precipitation method, absorption method, coagulation sedimentation, counter-infiltration at present
Method, ion-exchange, electrochemical treatment etc..In numerous processing methods, chemical precipitation method, absorption method and coagulation sedimentation
Due to the advantages that treatment effect is stable, technique is simple, operating cost is low, treating capacity is big, suitable treatment high-concentration fluorine-containing waste water, it is
Current most important fluoride wastewater treatment technical method.
The precipitation method and absorption method relied primarily in processing procedure add a large amount of chemical agents formed fluoride precipitation or
Fluoride adsorbs forms co-precipitation on the surface of sediment, or the fluorine ion gone in a manner of physics and chemisorbed in water removal,
Fluorine ion in water removal is removed finally by the mode of separation of solid and liquid.Stirring intensity, reaction time, fluoride waste in this course
The technological parameters such as initial concentration, pH and technical process are an important factor for influenceing defluorination effect.Because whole process needs to use
A large amount of chemical agents, thus the expense of chemical agent turns into the important sources of whole processing technology cost.Therefore, develop new
, the treatment agent that cost is lower, more environment-friendly be this field important research direction.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide discarded concrete in removing fluorine from water
Using to solve the problems, such as that existing a large amount of discarded concrete produces secondary pollution, while solving existing chemical agent fluorine removal cost
The problem of high.
To achieve the above object, the present invention adopts the following technical scheme that：
The invention discloses application of the discarded concrete in removing fluorine from water, method is as follows during application：
（1）Using discarded concrete as raw material, after just broken, calcining, Behavior of Hardened Cement Paste is filtered out, will be selected after the Behavior of Hardened Cement Paste ball milling
Powder separates, and particle of the collection cut size below 80 μm, obtains removing fluorine from water agent；
（2）By step（1）In obtained removing fluorine from water agent input fluoride waste fluorine removal can be carried out to waste water.
Preferably, step（1）In just it is broken after discarded concrete particle diameter in below 10mm.Concrete particle diameter after just broken
It is smaller, be more advantageous to calcine, be easy to filter out Behavior of Hardened Cement Paste from concrete.
Preferably, step（1）Described in calcination condition be：5 ~ 8 DEG C/min speed is warming up to 200 ~ 400 DEG C, constant temperature
Natural cooling after 10 ~ 30min.Calcining can weaken the adhesion strength of aggregate and Behavior of Hardened Cement Paste in discarded concrete, in order to by water
Mudstone is screened from concrete, can be calcined using Muffle furnace, and electromagnetic type concussion pulverizer can be used to carry out after calcining
Concussion separation.
Preferably, step（1）Surfactant is added in Behavior of Hardened Cement Paste mechanical milling process, the surfactant is lignin
At least one of sulfonate, ethylene glycol and triisopropanolamine, wherein lignosulfonates, ethylene glycol, triisopropanolamine plus
Enter amount is respectively the Behavior of Hardened Cement Paste quality 0.06 ~ 0.1%, 0.02 ~ 0.1%, 0.03 ~ 0.1%..Ball milling can further increase water
The microstructural flaws of mudstone, increase its surface area, ball milling effect can be improved by adding surfactant.
Preferably, Ball-milling Time is 20 ~ 50min.
As preferential, step（2）The quality of the removing fluorine from water agent of middle input and the mass ratio of fluorinion in waste water be 30 ~
550:1。
Preferably, step（2）The middle fluorine removal time is 5 ~ 30min.
Preferably, step（2）Mixing speed is 40 ~ 200r/min during middle fluorine removal.
Preferably, step（2）It is 5 ~ 6 that wastewater pH is adjusted during middle fluorine removal.
Compared with prior art, the present invention has the advantages that：
1st, the present invention prepares one kind by the applications expanding of discarded concrete this building castoff to fluoride waste improvement field
Water body fluoride removal material, its reaction speed during removing fluorine from water is fast, and in the absence of limit doped amount, utilization ratio is high, defluorination effect
It is stable, it can at room temperature operate, improve the resource utilization efficiency of waste water mudstone, also be hardened cement in discarded concrete
The high value added utilization of stone provides a Technology Ways, avoids discarded concrete in the prior art and is preparing regeneration concrete
Material, building block or again during calcination of cement clinker high porosity, high water absorbing capacity, low-intensity, volume are limited etc. brings
The problem of.
2nd, the present invention prepares removing fluorine from water agent using discarded mixed mud, and raw material sources are extensive, cost is cheap, and this is flood tide
The recycling of discarded concrete provides a new approach；Also it is fluorine-containing useless for China river, lake, industry and life etc.
The improvement of water provide it is a kind of it is easy to operate, applied widely, cost is cheap, the green, technique that " can control poison with useless "
Method；It meets the strategic requirement of national development recycling economy, enjoys national and local related industry policy support, has wide
Development and application prospect.
3rd, the present invention isolates Behavior of Hardened Cement Paste from discarded concrete, and removing fluorine from water agent is made after Behavior of Hardened Cement Paste is milled, wherein,
The Behavior of Hardened Cement Paste filtered out from discarded concrete, its main thing phase composition are hydrated calcium silicate gel（C-S-H）, entringite
（AFt）And unhydrated dicalcium silicate（C2S）Deng calcium containing compound.In the case of full water, C-S-H gels have very big in itself
Specific surface area, after ball milling is scattered microdefect increase, specific surface area increase, active site position further increases.This knot
Structure is on the one hand so that calcareous cement hydrated product easily interacts with hydrone so that calcium ion is extracted into fluorinated water
In solution, with the F in fluoride waste-CaF precipitations are combined to form, and are separated out from fluoride waste；On the other hand, in fluoride waste
F-C-S-H gel surfaces are easily adsorbed at, then are removed through subsequent filter, under the effect of above-mentioned both sides, and then can be effective
Remove the fluorine ion in water.
4th, the removing fluorine from water agent that the present invention is prepared using discarded mixed mud, to the initial concentration adaptability of fluoride waste compared with
Extensively, whether low concentration or high-concentration fluorine-containing waste water can effectively remove fluorine ion therein, under treatment conditions of the present invention,
The clearance of fluoride waste is up to 95%.
Brief description of the drawings
Fig. 1 is the defluorination effect figure of removing fluorine from water agent difference dosage prepared by embodiment 2；
Fig. 2 is the defluorination effect figure of removing fluorine from water agent different disposal time prepared by embodiment 2；
Fig. 3 is the defluorination effect figure of removing fluorine from water agent difference speed of agitator prepared by embodiment 2；
Defluorination effect figures of the Fig. 4 for removing fluorine from water agent prepared by embodiment 2 to the fluoride waste of different initial concentrations；
Fig. 5 is the defluorination effect figure of the removing fluorine from water agent of the preparation of embodiment 2 at various ph values；
Fig. 6 is removing fluorine from water agent particulate scan electron microscope prepared by embodiment 2；
Fig. 7 is the energy spectrum analysis of particle before removing fluorine from water agent fluorine removal prepared by embodiment 2（EDS）Spectrogram；
Fig. 8 is the energy spectrum analysis of precipitated product after removing fluorine from water agent fluorine removal prepared by embodiment 2（EDS）Spectrogram.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
Fluoride waste is handled using discarded concrete, prepares removing fluorine from water agent first with discarded concrete, step is as follows：
（1）Discarded concrete is chosen from building waste, and it is broken at the beginning of small-sized hammer mill is carried out, controlled with square hole screen just broken
Particle diameter d≤10mm of discarded concrete afterwards, it is just broken after discarded concrete is fitted into Muffle furnace progress low temperature precalcining, with decrease
The adhesion strength of aggregate and Behavior of Hardened Cement Paste in discarded concrete, specific calcination condition are：200 DEG C are warming up to 6 DEG C/min speed,
25 DEG C are naturally cooled to after constant temperature 20min.
（2）Discarded concrete after calcining is subjected to concussion processing in electromagnetic type shakes pulverizer, to carry out coarse aggregate
With the separation of waste water mudstone, separating obtained Behavior of Hardened Cement Paste is added in ball mill and is ground, further to increase its microcosmic knot
Structure defect, increase its specific surface area, in order to improve grinding effect, the second two of Behavior of Hardened Cement Paste quality 0.06% is added in process of lapping
Alcohol carries out Dispersion on surface processing；It is 40min to control Ball-milling Time simultaneously.
（3）Material after grinding because physical property difference will produce " split-phase ", using gas flow sizing machine select powder and point
From the particle of collection cut size≤80 μm produces removing fluorine from water agent.
Removing fluorine from water agent obtained above is put into fluoride waste and carries out fluorine removal, fluorinion in waste water initial concentration is
200mg/l, treatment conditions are：The mass ratio of removing fluorine from water agent and fluorine ion is 442:1, processing time 5min, mixing speed
For 200r/min, wastewater pH is 5 ~ 6, and after processing, fluorinion in waste water concentration is 12.5mg/l.
Embodiment 2
Removing fluorine from water agent is prepared first with discarded concrete, step is as follows：
（1）Discarded concrete is chosen from building waste, and it is broken at the beginning of small-sized hammer mill is carried out, controlled with square hole screen just broken
Particle diameter d≤10mm of discarded concrete afterwards, it is just broken after discarded concrete is fitted into Muffle furnace progress low temperature precalcining, with decrease
The adhesion strength of aggregate and Behavior of Hardened Cement Paste in discarded concrete, specific calcination condition are：400 DEG C are warming up to 8 DEG C/min speed,
20 DEG C are naturally cooled to after constant temperature 20min.
（2）Discarded concrete after calcining is subjected to concussion processing in electromagnetic type shakes pulverizer, to carry out coarse aggregate
With the separation of waste water mudstone, separating obtained Behavior of Hardened Cement Paste is added in ball mill and is ground, further to increase its microcosmic knot
Structure defect, increase its specific surface area, in order to improve grinding effect, the wooden of Behavior of Hardened Cement Paste quality 0.08% is added in process of lapping
Plain sulfonate, 0.06% ethylene glycol and 0.06% triisopropanolamine carry out Dispersion on surface processing；The Ball-milling Time is controlled to be simultaneously
30min。
（3）Material after grinding because physical property difference will produce " split-phase ", using gas flow sizing machine select powder and point
From collection cut size≤80um particle produces removing fluorine from water agent.
Removing fluorine from water agent obtained above is put into fluoride waste and carries out fluorine removal, fluorinion in waste water initial concentration is
200mg/l, treatment conditions are：The mass ratio of removing fluorine from water agent and fluorine ion is 221:1, processing time 30min, mixing speed
For 200r/min, wastewater pH is 5 ~ 6, after handling 30min, stands 12h filterings, fluorinion concentration is 10mg/ in filtrates tested
l。
Fig. 6 is the microcosmic scanning electron microscope (SEM) photograph of removing fluorine from water agent particle prepared by embodiment 2, be can be seen that from figure, institute of the present invention
About 10 μm of the removing fluorine from water agent grain diameter of preparation, surface are mutual by a large amount of small flakeys and short cylinder hydrolysis product of cement
Interspersed overlap joint forms scramble network shape, loose porous, and specific surface area increase, active site position also further increases, and this is also this
The reason for removing fluorine from water agent prepared by invention can effectively remove fluorine ion in water.Table 1 is the removing fluorine from water agent prepared by embodiment 2
Chemical composition.
The chemical composition of removing fluorine from water agent prepared by table 1（wt%）
| SiO2 | CaO | Al2O3 | Fe2O3 | MgO | K2O | NaO | SO3 | TiO2 |
| 48.8295 | 30.7955 | 8.9764 | 3.8741 | 1.5689 | 1.6376 | 1.0428 | 2.0102 | 0.7680 |
Filter residue after being filtered in embodiment 2 is dried in vacuo at 105 DEG C, dried sample carries out EDS power spectrum tests, with
The fluorine removal mechanism of removing fluorine from water agent of the present invention is analyzed, Fig. 7 and Fig. 8 are respectively the power spectrum of removing fluorine from water agent before and after reacting（EDS）Point
Analysis figure.It was found from figure, compared with before reaction, removing fluorine from water agent particle surface X-ray energy spectrum after reaction（EDS）In occur it is obvious
Fluorine element diffraction maximum, the F after this explanation reaction in solution-It is adsorbed or water body fluoride removal material is deposited in the form of calcirm-fluoride
Surface, so as to be removed from solution.
The determination of optimal processing parameter：
（1）In order to determine optimum dosage, a certain amount of pure NaF of analysis is accurately weighed, and the fluorine-containing of 200mg/l is configured with volumetric flask
Simulated wastewater, measure the above-mentioned fluorine-containing simulated wastewaters of 100ml successively with graduated cylinder in 6 clean beakers, at the same sequentially add 0.5g,
Removing fluorine from water agent prepared by 1.0g, 2.0g, 3.0g, 4.0g, 5.0g embodiment 2, fluorine removal reaction is carried out using magnetic stirring apparatus.Remove
It is 200r/min that stirring intensity is controlled during fluorine, is removed after reacting 30min at room temperature from magnetic stirring apparatus, stands 12 hours
After filter.According to National Standard of the People's Republic of China《The measure ion selective electrode method of water quality fluoride（GB7484-
1987）》Specified in method, the concentration of fluorine ion in filtrate is determined using fluoride ion selective electrode, with living prepared by sign
The practical effect of property fluorine removal particle, experimental result are as shown in Figure 1.
As seen from Figure 1, when removing fluorine from water agent dosage is 0.5g, the waste water fluoro-containing concentration after processing is 21mg/l, is thrown
When dosage is 1g, the waste water fluoro-containing concentration after processing is 20mg/l, when dosage increases to 2g, the waste water fluoro-containing concentration after processing
For 10mg/l, when dosage continues to increase to 5g, the waste water fluoro-containing concentration after processing is only 5mg/l, it is seen that dosage is more than 2g
Afterwards, continuing increases dosage influences less on treatment effect, and it is that 2g is optimum dosage to consider dosage, that is, the water added
The mass ratio of body defluorinating agent and fluorinion in waste water is 221:1.
（2）The determination of optimum reacting time, measure the fluorine-containing simulated wastewater 100ml that concentration is 200mg/l successively with graduated cylinder
In 6 clean beakers, sequentially add 4.0g embodiments 2 and prepare removing fluorine from water agent, be placed on magnetic stirring apparatus to enter at room temperature
Row fluorine removal is reacted, and it is 200r/min to control stirring intensity, reacts 5min, 10min, 15min, 20min, 25min, 30min successively
After remove beaker, filtered after standing 12h, the fluorinion concentration of supernatant after test filtering, to determine optimum reacting time, as a result
As shown in Figure 2.
It was found from figure, with the increase in reaction time in preceding 5min, F in waste liquid-Concentration rapid decrease, after 5min with
The increase in reaction time, F in waste liquid-Concentration, which declines, to ease up, and is held essentially constant, it is contemplated that actual production efficiency, may be selected
5min is optimum reacting time.
（3）The determination of optimal stirring intensity, the fluorine-containing simulated wastewater 100ml that concentration is 200mg/l is measured with graduated cylinder successively
In 9 clean beakers, the removing fluorine from water agent of the preparation of 4.0g embodiments 2 is sequentially added, is placed on magnetic stirring apparatus at room temperature
Fluorine removal reaction is carried out, changes stirring intensity, is set to 200r/min, 190r/min, 170r/min, 150r/min, 100r/
Min, 80r/min, 40r/min, 30min is reacted, filtered after standing 12h, the fluorinion concentration of supernatant after test filtering, with true
Fixed optimal stirring intensity, as a result as shown in Figure 3.It can be seen that stirring intensity influences less on defluorination effect, it is contemplated that power
Energy consumption, select 40r/min.
（4）Fluorine-containing waste liquid initial concentration（C0）Influence to defluorination effect, measured respectively with graduated cylinder concentration be 200mg/l and
20mg/l fluorine-containing simulated wastewater 100ml sequentially adds the removing fluorine from water agent of the preparation of 4.0g embodiments 2 in 2 clean beakers,
It is placed on magnetic stirring apparatus and carries out fluorine removal reaction at room temperature, speed of agitator 200r/min, react 30min, stands mistake after 12h
Filter, the fluorinion concentration of supernatant, experimental result are as shown in Figure 4 after test filtering.It was found from figure, prepared removing fluorine from water agent pair
The initial concentration adaptability of fluoride waste is wider, and whether low concentration or high-concentration fluorine-containing waste water can be removed effectively therein
Fluorine ion so that go out water fluoridation and be reduced to reduced levels, and the lower water outlet fluorinion concentration of concentration is lower.
（5）Optimum response pH determination, fluorine-containing simulated wastewater 100ml that concentration is 200mg/l is measured successively with graduated cylinder in 2
In individual clean beaker, research system is in differential responses pH（PH=5 ~ 6 and pH=11 ~ 12）Under the conditions of fluorine removal practical effect,
Two systems respectively add the removing fluorine from water agent of the preparation of 4.0g embodiments 2, are placed on magnetic stirring apparatus and carry out fluorine removal reaction at room temperature,
Speed of agitator is 200r/min, reacts 30min, is filtered after standing 12h, the fluorinion concentration of supernatant after test filtering, as a result
As shown in Figure 5.It was found from figure, under the conditions of differential responses pH, prepared defluorinating agent has preferable defluorination effect.When pH=11 ~ 12
When, as the concentration of the progress fluoride waste of reaction is reduced to 40mg/L or so, clearance has reached nearly 80%, anti-when system
When answering the pH to be reduced to 5 ~ 6, as the concentration of the progress fluoride waste of reaction is reduced to below 10mg/L, clearance has reached 95%.
It can be seen that optimal reaction condition is advisable with acid system, pH controls are preferred 5 ~ 6.
From testing above, the present invention is using the more excellent condition of discarded concrete processing fluoride waste：Speed of agitator
40r/min, wastewater pH are 5 ~ 6, processing time 5min, and the removing fluorine from water agent of input and the mass ratio of fluorine ion are 221:1.
The above embodiment of the present invention is only example to illustrate the invention, and is not the implementation to the present invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all embodiments can not be exhaustive.It is every to belong to technical scheme
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (10)
1. application of the discarded concrete in removing fluorine from water.
2. application according to claim 1, it is characterised in that method is as follows during application：
（1）Using discarded concrete as raw material, after just broken, calcining, Behavior of Hardened Cement Paste is filtered out, will be selected after the Behavior of Hardened Cement Paste ball milling
Powder separates, and particle of the collection cut size below 80 μm, obtains removing fluorine from water agent；
（2）By step（1）In obtained removing fluorine from water agent input fluoride waste fluorine removal can be carried out to waste water.
3. application according to claim 2, it is characterised in that step（1）In just it is broken after discarded concrete particle diameter exist
Below 10mm.
4. application according to claim 2, it is characterised in that step（1）Described in calcination condition be：5 ~ 8 DEG C/min's
Speed is warming up to 200 ~ 400 DEG C, natural cooling after 10 ~ 30min of constant temperature.
5. application according to claim 2, it is characterised in that step（1）Sulfomethylated lignin is added in Behavior of Hardened Cement Paste mechanical milling process
At least one of hydrochlorate, ethylene glycol and triisopropanolamine surfactant, wherein lignosulfonates, ethylene glycol, three isopropyls
The addition of hydramine is respectively 0.06 ~ 0.1%, 0.02 ~ 0.1%, the 0.03 ~ 0.1% of the Behavior of Hardened Cement Paste quality.
6. application according to claim 5, it is characterised in that Ball-milling Time is 20 ~ 50min.
7. according to the application described in any one of claim 2 to 6, it is characterised in that step（2）The removing fluorine from water agent of middle input
The mass ratio of quality and fluorinion in waste water is 30 ~ 550:1.
8. according to the application described in any one of claim 2 to 6, it is characterised in that step（2）The middle fluorine removal time is 5 ~ 30min.
9. according to the application described in any one of claim 2 to 6, it is characterised in that step（2）Mixing speed is 40 during middle fluorine removal
~200r/min。
10. according to the application described in any one of claim 2 to 6, it is characterised in that step（2）Wastewater pH is adjusted during middle fluorine removal
For 5 ~ 6.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108892221A (en) * | 2018-06-21 | 2018-11-27 | 湖南双晟科技信息咨询有限公司 | A method of water body fluoride removal material is prepared using solid waste |
| CN109574059A (en) * | 2019-01-24 | 2019-04-05 | 长江师范学院 | A kind of preparation method of calcium carbonate fine powder |
| CN109621925A (en) * | 2019-01-24 | 2019-04-16 | 长江师范学院 | A kind of collecting carbonic anhydride agent and its application |
| CN109675517A (en) * | 2018-12-11 | 2019-04-26 | 西安建筑科技大学 | A kind of high temperature modified high alumina cement de-fluoridation adsorbent, preparation method and applications |
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| CN106365281A (en) * | 2016-10-24 | 2017-02-01 | 长江师范学院 | Preparation method of water phosphate removing agent and water phosphate removing method |
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| CN106365281A (en) * | 2016-10-24 | 2017-02-01 | 长江师范学院 | Preparation method of water phosphate removing agent and water phosphate removing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892221A (en) * | 2018-06-21 | 2018-11-27 | 湖南双晟科技信息咨询有限公司 | A method of water body fluoride removal material is prepared using solid waste |
| CN109675517A (en) * | 2018-12-11 | 2019-04-26 | 西安建筑科技大学 | A kind of high temperature modified high alumina cement de-fluoridation adsorbent, preparation method and applications |
| CN109574059A (en) * | 2019-01-24 | 2019-04-05 | 长江师范学院 | A kind of preparation method of calcium carbonate fine powder |
| CN109621925A (en) * | 2019-01-24 | 2019-04-16 | 长江师范学院 | A kind of collecting carbonic anhydride agent and its application |
| CN109621925B (en) * | 2019-01-24 | 2021-09-28 | 长江师范学院 | Carbon dioxide trapping agent and application thereof |
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