CN105836783B - A kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method - Google Patents
A kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method Download PDFInfo
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- CN105836783B CN105836783B CN201610171852.6A CN201610171852A CN105836783B CN 105836783 B CN105836783 B CN 105836783B CN 201610171852 A CN201610171852 A CN 201610171852A CN 105836783 B CN105836783 B CN 105836783B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method, including optimization SO4 2‑Concentration, synchronous organics removal and heavy metal ion, calcium source original position sustained release and and F‑Ion quickly generates high-purity C aF2Precipitation；High-concentration fluorine-containing waste water comes from etching procedure, and preprocessing process includes removing SO4 2‑、H2O2Organics removal and charcoal absorption metal foreign ion；Using impurity from method for crystallising, promote calcirm-fluoride crystalline growth,, can slow mechanism dissolved release Ca with reference to fluoride waste with thin layer by CaO surfaces using CaO as calcium source2+Ion, with F‑React generation CaF2Precipitation.The present invention uses multisection type handling process, to reclaim the fluorine resource in the high-concentration waste water that etching procedure is produced in the form of calcirm-fluoride, both the processing cost of enterprise's fluoride waste had been reduced, it turn avoid the loss of fluorine resource, improve the purity for preparing calcirm-fluoride, the problem that little particle calcirm-fluoride is difficult to sedimentation separation is solved, the cascade utilization of fluorine recycling is realized, the full dose recycling of waste water of the fluoro-containing concentration more than 50mg/L is completed.
Description
Technical field
The present invention relates to a kind of fluorine its recovery method as resource, and in particular in high-concentration fluorine-containing waste water, prepared by high-purity calcirm-fluoride
And the method for separation, belong to environmental technology field.
Background technology
Contain in the waste water of industrial discharge in substantial amounts of fluoride, such as waste discharge of glass manufacture industry, fluoride contains
Amount reaches 194-1980mg/L, produces the fluorinated volume of chemical plant emission waste water of fluoric acid in more than 1000mg/L, phosphate fertilizer plant is fluorine-containing
Fluorinated volume reaches in waste water all contains in 1500mg/L, the waste water of the industry such as production of electronic components, electroplating operations, metal smelt discharge
High concentration fluoride, wherein in production of electronic components industry, fluoride waste yield is big, mainly comes from matting, etching
Process.By taking the fluoride waste that etching procedure during Electronics Factory's chip production and matting are produced as an example, ion contained therein,
Except F-In addition, the also SO containing higher concentration4 2-, organic matter, and micro metal impurities ion etc..For fluorine and its chemical combination
Toxic action of the thing to the mankind, China provides that Oil repellent suitable in Drinking Water is 0.5-1.0mg/L.According to《Sewage is comprehensive
Close discharge standard》Primary standard is provided in GB8978-1996：Inorganic fluorine compounds highest allows concentration of emission in industrial wastewater
For 10mg/L.
The processing method of fluoride waste is more both at home and abroad at present, and these methods can be divided into two major classes：The precipitation method and absorption method.
Chemical precipitation/coagulating treatment is the main method of the industrial fluoride waste of processing, and typically fluoride waste is adjusted to optimum pH,
Calcium salt is added, so as to form the sludge of calcium fluoride containing.Conventional calcium salt is CaCl2、Ca(OH)2、CaCO3.Due to calcium fluoride particles
It is smaller, it is difficult to precipitate, it will usually after precipitation is formed, to take the method for adding flocculant, the calcium fluoride sludge moisture content of formation
It is higher, the sludge that especially inorganic fluoriding factory produces, wherein fluorination calcium component only accounts for 60% or so.Cheap calcium carbonate is made in addition
Go to precipitate fluorine for calcium source release calcium, release efficiency is low, had both caused the waste of calcium carbonate material, and had also increased sludge quantity, reduces
Calcium fluoride sludge content.The calcium fluoride sludge inorganic content of this method formation is high, and moisture content is higher, it is difficult to is dehydrated, therefore burns
Burn and landfill stabilization has a more problem, and according to《National dangerous waste register》Middle HW32 bars regulation, partially fluorinated calcium sludge category
In hazardous waste, therefore can not direct landfill disposal.
Calcirm-fluoride is again industrially a kind of highly important ore.Fluorite, also known as fluorite, main component are fluorinations
Calcium (CaF2), the ore is one of 20 several important nonmetallic ore raw materials in the world.With science and technology and national economy not
Disconnected development, fluorite turns into raw mineral materials important in modern industry.Fluorite ore is mainly used in metallurgy industry, chemical industry, its
Purposes can be used as the raw material needed for cosolvent, Acid of Hydrofluoric Acid Production, opacifier etc..Fluorite mineral deposits about 5 are verified in the current world
Hundred million tons, Chinese fluorite reserves are 21,000,000 tons, are only second to South Africa, Mexico.But Chinese high-grade fluorite ore ratio is small, mineral intergrowth
Many, exploitation for many years causes domestic fluorite rich ore to reduce increasingly, and largely should in fields such as chemical industry, metallurgy due to fluorite
With so that fluorite ore resource consumption is too fast, and because belonging to non-renewable ore resources, world's fluorite ore resources are precarious.
In view of the necessity of fluoride wastewater treatment, and the conventional lime precipitation method not only cause the waste of fluorine resource, and
Great environmental risk is brought, current fluoride waste fluid bed crystallisation directly prepares calcirm-fluoride, and it has gained fluorination
Calcium purity is not high, and calcium carbonate releases the low shortcoming of ca efficiency.At Chinese patent " a kind of processing of fluoride waste and device "
(CN101941752B) in, it was recently reported that the method for utilization fluid bed crystallization reactor, it is used adds crystal seed outside, forms bulky grain
Calcirm-fluoride, need to additionally add crystal seed.
Compared with prior art, it is contemplated that removing the foreign ion of fluoride waste, calcium is used as by the use of cheap lime
Source, the condition of optimization calcirm-fluoride formation, prepares high-quality calcirm-fluoride, and reclaiming calcirm-fluoride resource is used for the industries such as chemical industry.
The content of the invention
Present invention aims at prepare high-purity CaF there is provided a kind of high-concentration fluorine-containing waste water multistep treatment original position2Method,
By controlling foreign ion SO4 2-Concentration, reduction waste water in content of organics and foreign metal ion, while using life
Into CaSO4It is used as follow-up CaF2The crystal seed of generating process, Ca is discharged using original position2+And and F_Ion is reacted, so as to promote
Its generation purity is high, particle diameter is big, the CaF of free settling2Particle, reclaims the highly concentrated of etching procedure generation in the form of being fluorinated calcium product
The fluorine resource spent in waste water, had both reduced the processing cost of enterprise's fluoride waste, the loss of fluorine resource is avoided again.
The present invention is achieved by the following technical solutions：
A kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method, including optimization SO4 2-It is concentration, same
Walk organics removal and heavy metal ion, calcium source original position sustained release and and F-Ion quickly generates high-purity C aF2Precipitation.
Described high-concentration fluorine-containing waste water comes from etching procedure and matting production during IC Chip Production
Raw fluoride waste, wherein, F-For 1000-3000mg/L, SO4 2-Concentration is 300-500mg/L, and TOC is 15-40mg/L, and
Trace metal ion is 5-30mg/L, and the trace metal ion includes Cu2+、Ni+And Al3+。
Described optimization SO4 2-Concentration refers to, is realized by adding barium salt, and the dosage of the barium salt is thrown for theoretical molar
SO after 0.7-0.8 times of dosage, processing4 2-Concentration is controlled in 60-150mg/L.
Described synchronous organics removal and heavy metal ion refer to, using heterogeneous Fenton reaction, H2O2Add dense
Degree control is in 50-150mmol/L, and rich in the control of iron activated carbon dosage in 1-3g/L, the reaction time is 20-40min, water outlet
TOC controls are controlled in 1-10mg/L in 1-10mg/L, trace metal ion concentration.
Described is rich in iron activated carbon, and its BET is 300-800cm2/ g, Fe load capacity are 10-30mg/g.
Described calcium source original position sustained release and and F-Ion quickly generates high-purity C aF2Precipitation refers to, utilizes effluent recycling control
System water inlet fluoro-containing concentration is in 200-350mg/L, and effluent recycling is than controlling in 4-7, [Ca2+]/[F-] it is 1.0-1.4, pH is 7-9,
Ca2+With F after plasma diffusing W,Mo-Reaction generation CaF2。
Described high-purity C aF2For graininess, its purity is 85-95%, and grain diameter is 0.3-0.8mm.
The present invention is by controlling SO in original waste water4 2-The concentration of plasma, with the CaSO of generation4It is used as follow-up CaF2Generation
The crystal seed of process, the organic matter and heavy metal ion in waste water is removed by means of heterogeneous Fenton, by the sustained release of quick lime
Ca in effect, control solution2+With F-Required Ion reaction equilibrium concentration, generation high-purity C aF2。
Compared with prior art, the invention has the advantages that：
1) for the water quality characteristic of etching waste water, the mode for taking multistage to pre-process removes impurity in fluoride waste, so that
Improve the purity of prepared calcirm-fluoride；
2) by controlling the flow velocity of impurity sulfate concentration and fluoride waste, content of organics is reduced, using part sulphur
Sour calcium nucleus in situ and CaF2In-situ two-step generating process, formed bulky grain calcium fluoride precipitate so that it is easily isolated；
3) high-concentration fluorine-containing waste water produced for etching procedure, realizes the cascade utilization of fluorine recycling, completes and contain
Funing tablet is more than the full dose recycling of 50mg/L fluoride waste.
Brief description of the drawings
Fig. 1 equips schematic diagram for the technological process of the present invention.
Wherein, 1 --- the first storage cistern, 2 --- barium salt solution groove, 3 --- mixed reaction pond, 4 --- centrifuge,
5 --- the second storage cistern, 6 --- absorbent charcoal adsorption tank, 7 --- lime beds, 8 --- vertical sedimentation basin.
Embodiment
High-purity CaF is prepared the invention provides a kind of high-concentration fluorine-containing waste water original position2Method, including foreign ion SO4 2-
Concentration optimization, the reduction of organic concentration, the removal of heavy metal ion, and release Ca in situ2+And and F-Ionic reaction
Process, realizes high-purity C aF2Preparation.
Described high-concentration fluorine-containing waste water, mostlys come from etching procedure and scavenger during IC Chip Production
The fluoride waste that sequence is produced, its F-Concentration is in 1000-3000mg/L, SO4 2-Concentration in 300-500mg/L, pH in the range of 1-5,
TOC is in 15-40mg/L, and foreign metal ion concentration is in 1-30mg/L.
Described optimization SO4 2-Concentration refers to, is added by barium salt, including BaCl2Or barium nitrate, dosage is theory
SO in 0.7-0.8 times of mole dosage, solution4 2-Concentration controls 60-150mg/L；The barium sulfate precipitate separation process of formation is adopted
With the pocket type centrifuge of periodic running, rotating speed need to reach 3000-5000rpm, and centrifugation time need to ensure in 5min.
Described synchronous organics removal and heavy metal ion refer to, using heterogeneous Fenton reaction, H2O2Add concentration
Control is in 50-150mmol/L, and pH controls are in 2-4, rich in iron activated carbon dosage in 1-3g/L, and activated carbon Fe load capacity is 10-
30mg/g, its BET is in 300-800cm2/ g, the reaction time is 20-40min.TOC of yielding water is controlled in 1-10mg/L, Cu2+、Ni+With
Al3+Plasma concentration is controlled in 1-10mg/L.
Described calcium source original position sustained release and and F-Ion quickly generates high-purity C aF2Precipitation refers to that process original position discharges
Ca2+With preparation CaF2Carried out in lime bed, following current utilizes effluent recycling by quick lime bed, coutroi velocity 30-60m/h
Control water inlet fluoro-containing concentration is in 200-350mg/L, and temperature control is at 20-60 DEG C, and pH is in 7-9, Ca2+With F after plasma diffusing W,Mo-Reaction
Generate CaF2。
Described following current quick lime bed reaction, effluent recycling is than control in 4-7, dissolubility Ca2+Concentration is controlled in 1.5-
2.5g/L, [Ca2+]/[F-] it is 1.0-1.4.
Described high-purity bulky grain CaF2Enter vertical sedimentation basin with water outlet, so as to reach separation of solid and liquid.Dehydration separation
CaF afterwards2Particle purity is between 85-95%, and grain diameter is 0.3-0.8mm.
Ca is released in pretreatment mode, original position associated with precipitating, aoxidize and adsorbing2+Afterwards with F-Reaction forms the mistake of calcium fluoride crystal
Journey, substantially increases the rate of recovery of calcirm-fluoride, by the use of cheap cheap quick lime as calcium source, reduces cost recovery, so that
Drastically increase social benefit and economic benefit.The present invention is improved to device simultaneously.
The high-concentration fluorine-containing waste water that the present invention is discharged suitable for electronic chip manufacturing enterprise.Its preparation method includes following step
Suddenly, Fig. 1 is referred to：
Step one, the high-concentration fluorine-containing waste water that etching procedure is produced is collected separately in the first storage cistern 1, is pumped into mixing anti-
Pond 3 is answered, is mixed with the certain density barium chloride or barium nitrate solution configured from barium salt solution groove 2, by sulphate moiety
Retain to 60-150mg/L, mixing speed is 300-500rpm, and the reaction time is 0.5h, form BaSO4After precipitation, water outlet is passed through
Centrifuge 4.
Step 2, water outlet enters after the second storage cistern 5, regulation pH=4 after step one reaction, by 50-150mmol/L amount
Add H2O2, absorbent charcoal adsorption tank 6 is pumped into afterwards, and the wherein filling of absorbent charcoal adsorption tank 6 is rich in iron charcoal, and its BET is 300-
800cm2/ g, Fe load capacity are 10-30mg/g, and the residence time is 20-40min, in absorbent charcoal adsorption tank 6 rich in iron charcoal it is enterprising under
Go out, it is ensured that continuous operation, usage amount is 1-3g/L；TOC of yielding water is controlled in 1-10mg/L, Cu2+、Ni+And Al3+Plasma concentration control
System is in 1-10mg/L.
Step 3, high-purity quick lime crosses 10 mesh sieves, it is ensured that its particle diameter is filled in lime bed in the range of 1.5-2mm, afterwards
7.Flow velocity is 30-60m/h, and effluent recycling ratio is 4-7, [Ca2+]/[F-] control is in the range of 1.0-1.4, by adjusting reflux ratio
It is 200-350mg/L to control water inlet fluoro-containing concentration, and pH is 7-9.
Step 4, CaF2Mutual nucleation or heterogeneous nucleation ultimately form bulky grain precipitation, thin of residual between fine grained
Grain continues to flow through precipitation reaction area with reflux solution；Bulky grain flows into vertical sedimentation basin 8 with current, falls into bottom V-type bucket,
Have a rest discharge, and waste water flows through after vertical sedimentation basin 8 discharge or further advanced treating.
Following embodiments are with the technical scheme is that premise, gives detailed embodiment and specifically operated
Journey.But protection scope of the present invention is not limited to following embodiments, for persons skilled in the art, without departing from this
Any obvious change done under the premise of inventive technique scheme, belongs to the protection domain of the claims in the present invention.
Embodiment 1
Former fluoride waste concentration is 3000mg/L, SO4 2-Concentration is 500mg/L, in addition containing with Cu2+Based on metal from
Son, content is below 30mg/L, and TOC contents are 40mg/L.
Step one, BaCl2Dosage is 0.7 times of theoretical value, remaining SO4 2-For 150mg/L.
Step 2, H2O2Dosage is 50mmol/L, after pH is adjusted to 4, by the Fe containing load2+Absorbent charcoal adsorption tank 6, it is living
Property charcoal usage amount in 1g/L, its BET is 300cm2/ g, Fe load capacity be 10mg/g, the residence time is 20min, each metalloid from
Sub- concentration is below 10mg/L, and TOC is down to 10mg/L.
Step 3, lime bed 7 induces CaF as fluoride waste2The reactor of crystallization, former fluoride waste is in reactor bottom
Mixed with recirculation water, [Ca of intaking2+]/[F-]=1.0mol/mol, use content for 90% CaO, water inlet fluorine load exist
2kgF-/m2H, reflux ratio is 7, and the initial Funing tablet of mixing water inlet is 350mg/L, hydraulic load 30m/h, and it reacts pH controls and existed
9 or so.
The CaF of discharge2Sludge content is 85%, and average grain diameter is 0.3mm.
Embodiment 2
According to carrying out same operation described in embodiment 1.Fluoride waste concentration is 1000mg/L, and sulfate concentration is
300mg/L, TOC content are 25mg/L, and metal ion key component is Cu2+, its concentration is less than 15mg/L.
Step one, barium chloride is added, its dosage is 0.8 times of theoretical value, and remaining sulfate concentration is 60mg/L.Generation
BaSO4It is deposited under vertical centrifugal machine 3000rpm speed and separates.
Step 2, H2O2Dosage is 150mmol/L, after pH is adjusted into 4, by the Fe containing load2+Absorbent charcoal adsorption tank
6, activated carbon usage amount is 3g/L, and BET is 500cm2/ g, Fe load capacity are 20mg/g, and the residence time is to go out after 30min, absorption
Water TOC contents are down to below 10mg/L, Cu2+Ion concentration is below 10mg/L.
Step 3, into the lime bed 7 containing calcium oxide, [Ca2+]/[F-]=1.4, upflow velocity is 60m/h, where reaction
PH controls 7, initial Funing tablet lowest part of intaking is only 200mg/L, and reflux ratio is 4, and the initial Funing tablet of mixing water inlet is
200mg/L, it reacts pH controls 7.
The calcium fluoride particles particle diameter of formation is in 0.5mm or so, and sludge Calcium Fluoride Content is 90%.
Embodiment 3
According to carrying out same operation described in embodiment 1, but processing water is different, control condition and parameter phase not to the utmost
Together.Fluoride waste concentration is 1800mg/L, and sulfate concentration is 430mg/L, and TOC contents are 15mg/L, Cu2+Concentration is 5mg/L.
Step one, barium salt uses BaCl2, its dosage is 0.75 times of theoretical value, remaining SO4 2-For 110mg/L.
Step 2, H2O2Dosage is 100mmol/L, after pH is adjusted into 4, by the Fe containing load2+Absorbent charcoal adsorption tank
6, activated carbon dosage is 2g/L, and its BET is 800cm2/ g, Fe load capacity are 30mg/g, and the residence time is to go out after 40min, absorption
Water Cu2+Residual concentration is 1mg/L, and TOC contents are down to 1mg/L.
Step 3, into the lime bed 7 containing calcium oxide, [Ca2+]/[F-]=1.2, reflux ratio is 5, and upflow velocity is 50m/
H, minimum initial Funing tablet of intaking is only 250mg/L, and reaction pH controls are at 8, and the clearance of fluorine is up to 97%, the fluorination of formation
Calcium grain diameter is in 0.8mm or so, and sludge Calcium Fluoride Content is up to 95%.
Claims (7)
1. a kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method, it is characterized in that, including optimization SO4 2-It is dense
Degree, synchronous organics removal and heavy metal ion, calcium source original position sustained release and and F-Ion quickly generates high-purity C aF2Precipitation；
Its process is：
First pass through and add SO in barium salt optimization fluoride waste4 2-Concentration is in 60-150mg/L, in favor of being formed with CaSO4To be endogenous micro-
The CaF of nucleus2Precipitation, synchronously uses heterogeneous Fenton reaction so that TOC of yielding water control in 1-10mg/L, trace meter from
Sub- concentration control finally realizes calcium source original position sustained release in 1-10mg/L using lime bed, fluorine-containing by effluent recycling control water inlet
Concentration is in 200-350mg/L, so as to generate high-purity CaF2Sediment.
2. high-concentration fluorine-containing waste water multistep treatment original position according to claim 1 prepares high-purity CaF2Method, its feature
It is that what described high-concentration fluorine-containing waste water came from that etching procedure and matting during IC Chip Production produce contains
Fluorine waste water, wherein, F-For 1000-3000mg/L, SO4 2-Concentration is 300-500mg/L, and TOC is 15-40mg/L, and micro gold
Category ion is 5-30mg/L, and the trace metal ion includes Cu2+、Ni+And Al3+。
3. high-concentration fluorine-containing waste water multistep treatment original position according to claim 1 prepares high-purity CaF2Method, its feature
It is that the dosage of the barium salt is 0.7-0.8 times of theoretical molar dosage.
4. high-concentration fluorine-containing waste water multistep treatment original position according to claim 1 prepares high-purity CaF2Method, its feature
It is, in described heterogeneous Fenton reaction, H2O2Concentration control is added in 50-150mmol/L, rich in iron activated carbon dosage
Control is in 1-3g/L, and the reaction time is 20-40min.
5. high-concentration fluorine-containing waste water multistep treatment original position according to claim 4 prepares high-purity CaF2Method, its feature
It is that described is rich in iron activated carbon, and its BET is 300-800cm2/ g, Fe load capacity are 10-30mg/g.
6. high-concentration fluorine-containing waste water multistep treatment original position according to claim 1 prepares high-purity CaF2Method, its feature
It is that in described calcium source original position sustained release, effluent recycling is than controlling in 4-7, [Ca2+]/[F-] it is 1.0-1.4, pH is 7-9, Ca2+From
With F after son release-Reaction generation CaF2。
7. the high-concentration fluorine-containing waste water multistep treatment original position according to claim 1 or 6 prepares high-purity CaF2Method, it is special
Levying is, described high-purity C aF2For graininess, its purity is 85-95%, and grain diameter is 0.3-0.8mm.
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| CN106277005B (en) * | 2016-08-27 | 2017-08-01 | 盛隆资源再生（无锡）有限公司 | A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in the resource from calcium fluoride sludge |
| CN111661864A (en) * | 2020-07-21 | 2020-09-15 | 四川省乐山锐丰冶金有限公司 | Method for preparing high-purity calcium fluoride by using fluorine-containing wastewater |
| CN115784408B (en) * | 2022-08-31 | 2023-09-12 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by utilizing modified seed crystal induced crystallization |
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| EP0476773A1 (en) * | 1990-09-18 | 1992-03-25 | DHV Water B.V. | Method for the removal of fluoride from waste water |
| CN1244501A (en) * | 1998-07-15 | 2000-02-16 | 日本电气株式会社 | Treating apparatus for waste water containing fluoride and its method |
| CN101941752A (en) * | 2010-09-05 | 2011-01-12 | 中南大学 | Method and device for treating fluorine-containing waste water |
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2016
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|---|---|---|---|---|
| EP0476773A1 (en) * | 1990-09-18 | 1992-03-25 | DHV Water B.V. | Method for the removal of fluoride from waste water |
| CN1244501A (en) * | 1998-07-15 | 2000-02-16 | 日本电气株式会社 | Treating apparatus for waste water containing fluoride and its method |
| CN101941752A (en) * | 2010-09-05 | 2011-01-12 | 中南大学 | Method and device for treating fluorine-containing waste water |
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| Title |
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| 流化床结晶技术处理含氟废水研究进展;姜科;《污染防治技术》;20100630;全文 * |
| 铁铜催化剂非均相Fenton降解苯酚及机制研究;杨岳主等;《环境科学》;20130730;第2659页1.2节 * |
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