CN102145929A - Method for treating alkaline high-concentration fluorine-containing waste water - Google Patents
Method for treating alkaline high-concentration fluorine-containing waste water Download PDFInfo
- Publication number
- CN102145929A CN102145929A CN 201110047708 CN201110047708A CN102145929A CN 102145929 A CN102145929 A CN 102145929A CN 201110047708 CN201110047708 CN 201110047708 CN 201110047708 A CN201110047708 A CN 201110047708A CN 102145929 A CN102145929 A CN 102145929A
- Authority
- CN
- China
- Prior art keywords
- waste water
- fluorine
- reaction
- concentration
- concentration fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for treating high-concentration fluorine-containing waste water. The method is characterized in that: a mixture of calcium carbonate and calcium hydroxide is taken as a precipitant, the fluorine concentration of the fluorine-containing waste water is lowered below the national discharge standard of 10 mg/L in a single groove in negative-pressure environment at one time with a chemical precipitation method, and the precipitation property of calcium fluoride is changed, so that solid-liquid separation of a reaction product becomes easy. The method has the advantages of low price and small consumption of the precipitant raw material, short process flow and convenience for operation, and no pollution, can be used for effectively rapidly removing fluorine in the waste water under mild and easily-controlled condition, and is an environmentally-friendly method for treating high-concentration fluorine-containing waste water.
Description
Technical field
The present invention relates to a kind of method of handling trade effluent, specifically, relating to a kind of mixture with lime carbonate and calcium hydroxide is precipitation agent, by chemical precipitation method one step high-concentration fluorine-contained waste water is reduced to method below the discharging standards under negative pressure.
Background technology
The source of fluoride waste is wider, the oxygen difluoride of iron and steel, metal metallurgy smelting, plating, electronics, chemical fertilizer, electronic industry, nuclear industry and organic fluorine senior lubricant, rocket propellant, fluoridizes industry such as hydrazine, fluorinated refrigerant and all can produce.If deal with improperly, will serious environment pollution, HUMAN HEALTH is constituted a threat to.Therefore, be spreading of control fluoride pollution, fluorine content must not surpass 10 mgL in the waste water of national regulation discharging
-1(GB 8978-1996).
The method of handling fluoride waste is more, can roughly be divided into chemical deposition method, coagulation sedimentation and absorption method.Chemical deposition method because of have method simple, handle advantages such as convenient, that expense is low, and be widely used in during fluoride waste handles.The chemical settling fado is made precipitation agent with liming (calcium hydroxide), but large usage quantity, normally 2 ~ 4 of theoretical value times even bigger, and the settling time grow (greater than 24 hours), product separates also relatively difficulty.Also have with Wingdale (lime carbonate) and make precipitation agent, this method has the segregative advantage of product, but reaction is slow, and the precipitation agent consumption is also bigger than lime water law.In addition, these two kinds of precipitation agents all are difficult in 10 mgL that the fluorine content that directly will go out saliva in the single reaction groove is reduced to national requirements
-1Below, and need carry out secondary even tertiary treatment, this has prolonged flow process undoubtedly, has reduced efficient.In order to improve processing efficiency, can take in liming, to add the method for soluble calcium salt (as calcium chloride), but soluble calcium salt is as a kind of industrial chemicals, its price is more expensive relatively, this has increased the cost of wastewater treatment undoubtedly, in addition, has also introduced other harmful ions such as chlorion.The raw materials cost of coagulation sedimentation and absorption method and running cost are all expensive, wastewater treatment that can only the amount of carrying out is little, fluorine content is lower, at present can't large-scale application in handling industrial fluoride waste.
We handle alkaline fluoride waste in research and (contain a large amount of NH
4 +And NH
3) process in find that when using single liming to be precipitation agent, precipitated product is difficult to natural subsidence, centrifugation or vacuum filtration also the difficulty; When using single Wingdale to be precipitation agent, though the separation of precipitated product is relatively easy, the outlet water fluoride content after single groove is handled is obviously greater than 10 mgL
-1If select other ways, then economy reduces greatly.Therefore, seek the alkaline fluorine-containing processing method of industrial waste water that a kind of raw material is inexpensive, defluorination efficient, the product separation is easy, have extremely important environment and economic implications.
Summary of the invention
At above-mentioned situation, advantage in conjunction with lime carbonate and calcium hydroxide, it is the method that precipitation agent is handled alkaline high-concentration fluorine-contained waste water that the present invention will provide a kind of mixture with lime carbonate and calcium hydroxide, and the fluorine that sinks under the environment of negative pressure reaction can disposablely be reduced to 10 mgL with fluorine content
-1Below, product separates easily, and reaches total system and do not have discharging substantially.
Emphasis of the present invention has 3 points.First point is that the mixture with lime carbonate and calcium hydroxide is a precipitation agent, in high-effective defluorination, greatly reduces the separating difficulty of precipitated product.The solubleness of calcium hydroxide in water is bigger than lime carbonate, thereby the speed of reaction of precipitation fluorine is faster than lime carbonate.But it is gluey that calcium hydroxide mostly is in water, and the reaction after product is difficult to carry out solid-liquid separation.And the separation performance of lime carbonate is better, uses modern coating technology, is " nuclear " with lime carbonate promptly, and the Calcium Fluoride (Fluorspan) that precipitin reaction generates is deposited on the surface of " nuclear ", and the calcium salt complex body of formation " fluorine outside, carbon interior " helps last solid-liquid separation.Therefore, utilize the advantage of lime carbonate and calcium hydroxide, the two is mixed by a certain percentage, precipitin reaction is carried out fast, can realize the sharp separation of product again.Second emphasis of the present invention is to carry out precipitin reaction under subnormal ambient.Fluorine content is up to 14gL in the high-concentration fluorine-contained alkaline waste water of certain factory that the present invention is directed to
-1(with F
-Meter), also there are a large amount of NH simultaneously
4 +(the pH value is about 9) promptly can be considered fluorinated ammonium NH
4The solution of F, can carry out following chemical reaction with lime carbonate and calcium hydroxide:
2NH
4F+CaCO
3→CaF
2↓+2NH
3↑+CO
2↑
2NH
4F+Ca(OH)
2 → CaF
2 ↓+2H
2O+2NH
3↑
According to the thermodynamics of reactions theory,, (be CO in the body series if can in time remove the gas of reaction generation for the chemical reaction that has gas to generate
2And NH
3), reaction is carried out to the direction that generates gas to greatest extent.Therefore, during reaction process, we vacuumize a whole set of confined reaction system, make it to form subnormal ambient, and this helps the carrying out of heavy fluorine reaction.A large amount of CO that reaction generates
2And NH
3, absorb with liming and phosphoric acid respectively.Liming absorbs CO
2The reactant that the lime carbonate that the back generates can be used as heavy fluorine next time turns back to reactor; Phosphoric acid absorption of N H
3The primary ammonium phosphate that the back generates can be used as fertilizer or other purposes, non-secondary pollution.The 3rd emphasis of the present invention is the source of burning yellow phosphorus as phosphoric acid.The heavy reacted water outlet of fluorine is used to absorb the Vanadium Pentoxide in FLAKES behind the yellow phosphorus burning and makes phosphoric acid, can realize the recycle of total system water resources.Yellow phosphorus burning process liberated heat also can be used for adding heat sink fluorine reactor.
The objective of the invention is to realize by the technical scheme that constitutes by following measure:
(1) lime carbonate and calcium hydroxide are mixed by a certain percentage.
(2) mixture and the pending waste water with above-mentioned calcium cpd together adds in the closed reactor, and the fluorine that sinks at a certain temperature reaction keeps stirring.Total system keeps certain vacuum tightness between the reaction period.Reactor air outlet subordinate connects liming scrubbing bottle and phosphoric acid scrubbing bottle respectively step by step.
(3) along with the carrying out of reaction, in the reactor a large amount of bubbles can appear.After for some time, bubble disappears substantially, and reaction finishes.
(4) solidliquid mixture in the reactor is separated, detect the fluorinion concentration of liquid phase.
In the aforesaid method, the fluorinion concentration of certain pending waste water of factory is up to 14 gL
-1
In the aforesaid method, the excessive 10%(of total calcium of adding is promptly by theoretical 1.1 times of participation reactions that need the calcium amount) get final product.Wherein, the mass ratio of lime carbonate and calcium hydroxide is 0.5 ~ 2.0:1.According to experimental result, the calcium hydroxide proportion is big more, and defluorination effect is good more, but separates difficult more.Take all factors into consideration, the mass ratio of preferred lime carbonate and calcium hydroxide is 1 ~ 1.5:1.
In the aforesaid method, temperature of reaction is 60 ~ 80 ℃, preferred 65 ~ 70 ℃.Reaction temperature is spent low (less than 60 ℃), and Neutral ammonium fluoride is difficult in the water and decomposes; Temperature of reaction is too high, and energy consumption is bigger, and the liquid phase evaporation is serious, and the fluorine concentration in the final outlet water is risen.
In the aforesaid method, the reaction times is 100 ~ 130 minutes, preferred 110-120 minute.Reaction times is too short, and defluorination can not reach target; Reaction times surpassed after 130 minutes, continued having little effect of defluorination.
In the aforesaid method, the vacuum tightness of reaction system is-0.06 ~-0.08 MPa.Vacuum tightness is high more, is beneficial to the effusion of gas more, and reaction is carried out also just thoroughly more, but considers problems such as equipment loss and energy consumption, preferred-0.07 ~-0.075 MPa.
The solidliquid mixture pH value that reaction finishes in the post-reactor is about 7, detects the fluorinion concentration of liquid phase after the solid-liquid separation with fluoride ion selective electrode, all less than 10 mgL
-1, reach discharging standards.The all recyclable utilization of other by products.
The present invention compared with prior art has following characteristics:
1. as the defluorination reactant, raw material is cheap and easy to get with lime carbonate and calcium hydroxide mixture in the present invention, and, make reaction back solid-liquid separation easy by the precipitation rerum natura that changes Calcium Fluoride (Fluorspan).Total calcium consumption is compared additive method and is descended greatly, only is that 1.1 times of theoretical value get final product.
2. the present invention is in the certain vacuum degree by the negative pressure method of innovation by the control reaction system, and energy disposable direct fluorine content with high-concentration fluorine-contained waste water within a short period of time drops to 10 mgL
-1Below, need not second-stage treatment, flow process is short.
3. technological process of the present invention is simple, and operation is very easy, and it is effective to handle fluoride waste, and non-secondary pollution, does not have discharging substantially, is a kind of method of eco-friendly processing fluoride waste.
Description of drawings
The method of the invention is handled the process flow diagram of high-concentration fluorine-contained waste water.
Embodiment
The present invention is described in further detail below by embodiment, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following examples, and all technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1:
Get 10.66 g lime carbonate and 7.11 g calcium hydroxides (are CaCO
3: Ca (OH)
2Mass ratio is 1.5:1, total calcium excessive 10%), with fluorine content be 14 gL
-1Fluorine stoste 500mL mix, in encloses container, react.The real reaction temperature is 65 ± 2 ℃, vacuum tightness is-0.075～-0.078MPa, 120 minutes reaction times.After reaction finishes the solidliquid mixture in the reactor being carried out vacuum filtration, is 3.99 mgL with the fluorinion concentration of fluorine ion selective electrode determining filtrate
-1
Embodiment 2:
Get 10.66 g lime carbonate and 7.11 g calcium hydroxides (are CaCO
3: Ca (OH)
2Mass ratio is 1.5:1, total calcium excessive 10%), with fluorine content be 14 gL
-1Fluorine stoste 500mL mix, in encloses container, react.The real reaction temperature is 78 ± 2 ℃, vacuum tightness is-0.075～-0.08MPa, 120 minutes reaction times.After reaction finishes the solidliquid mixture in the reactor being carried out vacuum filtration, is 8.31 mgL with the fluorinion concentration of fluorine ion selective electrode determining filtrate
-1
Embodiment 3:
Getting each 8.62 g(of lime carbonate and calcium hydroxide is CaCO
3: Ca (OH)
2Mass ratio is 1:1, total calcium excessive 10%), with fluorine content be 14 gL
-1Fluorine stoste 500mL mix, in encloses container, react.The real reaction temperature is 60 ± 2 ℃, vacuum tightness is-0.075～-0.078MPa, 120 minutes reaction times.After reaction finishes the solidliquid mixture in the reactor being carried out vacuum filtration, is 2.40 mgL with the fluorinion concentration of fluorine ion selective electrode determining filtrate
-1
Claims (6)
1. the mixture with lime carbonate and calcium hydroxide is the method that precipitation agent is handled high-concentration fluorine-contained waste water, it is characterized in that lime carbonate and calcium hydroxide are mixed by a certain percentage, together add in the closed reactor with pending waste water then, under certain temperature of reaction, stir and sink fluorine and react; Reaction system keeps certain vacuum tightness in the reaction process; Treat that the certain hour afterreaction finishes.
2. the method for the high-concentration fluorine-contained waste water of processing as claimed in claim 1 is characterized in that pending waste water fluorine content is higher, can reach 14 gL
-1
3. the method for the high-concentration fluorine-contained waste water of processing as claimed in claim 1 is characterized in that adopting the mixture of lime carbonate and calcium hydroxide is precipitation agent, and the mass ratio of the two is 0.5 ~ 2.0:1, preferred 1 ~ 1.5:1.
4. the method for the high-concentration fluorine-contained waste water of processing as claimed in claim 1 is characterized in that temperature of reaction is 60 ~ 80 ℃, preferred 65 ~ 70 ℃.
5. the method for the high-concentration fluorine-contained waste water of processing as claimed in claim 1 is characterized in that the reaction times is 100 ~ 130 minutes, preferred 110 ~ 120 minutes.
6. the method for the high-concentration fluorine-contained waste water of processing as claimed in claim 1 is characterized in that the vacuum tightness in the controlling reactor is-0.06 ~-0.08 MPa, preferred-0.07 ~-0.075 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110047708 CN102145929A (en) | 2011-02-28 | 2011-02-28 | Method for treating alkaline high-concentration fluorine-containing waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110047708 CN102145929A (en) | 2011-02-28 | 2011-02-28 | Method for treating alkaline high-concentration fluorine-containing waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102145929A true CN102145929A (en) | 2011-08-10 |
Family
ID=44420425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110047708 Pending CN102145929A (en) | 2011-02-28 | 2011-02-28 | Method for treating alkaline high-concentration fluorine-containing waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102145929A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659277A (en) * | 2012-05-10 | 2012-09-12 | 杭州蓝然环境技术有限公司 | Ammonium fluoride wastewater treatment technique |
| CN102690000A (en) * | 2012-05-11 | 2012-09-26 | 湖北富邦科技股份有限公司 | Method for recovering phosphorus in phosphorus chemical wastewater by using struvite production technology |
| CN104768878A (en) * | 2012-11-07 | 2015-07-08 | 大林产业株式会社 | Method for treating waste water containing fluorine component |
| CN112744942A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Pretreatment method of fluorine-containing boron-containing wastewater |
| CN114950104A (en) * | 2021-02-25 | 2022-08-30 | 陕西青朗万城环保科技有限公司 | Treatment method of organic waste gas containing hydrogen fluoride and control system thereof |
-
2011
- 2011-02-28 CN CN 201110047708 patent/CN102145929A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《磷肥与复肥》 20020731 魏兰等 "含氟酸性废水的处理" 第20页左栏倒数第1行至右栏第4行 1-6 第17卷, 第4期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659277A (en) * | 2012-05-10 | 2012-09-12 | 杭州蓝然环境技术有限公司 | Ammonium fluoride wastewater treatment technique |
| CN102690000A (en) * | 2012-05-11 | 2012-09-26 | 湖北富邦科技股份有限公司 | Method for recovering phosphorus in phosphorus chemical wastewater by using struvite production technology |
| CN104768878A (en) * | 2012-11-07 | 2015-07-08 | 大林产业株式会社 | Method for treating waste water containing fluorine component |
| CN112744942A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Pretreatment method of fluorine-containing boron-containing wastewater |
| CN114950104A (en) * | 2021-02-25 | 2022-08-30 | 陕西青朗万城环保科技有限公司 | Treatment method of organic waste gas containing hydrogen fluoride and control system thereof |
| CN114950104B (en) * | 2021-02-25 | 2024-05-28 | 陕西青朗万城环保科技有限公司 | Treatment method of hydrogen fluoride-containing organic waste gas and control system thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Removal of nutrients from piggery wastewater using struvite precipitation and pyrogenation technology | |
| CN100491276C (en) | Combined treatment process for high-concentration ammonia nitrogen waste water | |
| CN103121772B (en) | A kind of processing method of phosphorus-containing wastewater | |
| CN103395910B (en) | A kind of Vacuum potassium carbonate desulfurization liquid waste treatment technology and device | |
| US20150315054A1 (en) | System for treating coal gasification wastewater, and method for treating coal gasification wastewater | |
| CN102145929A (en) | Method for treating alkaline high-concentration fluorine-containing waste water | |
| CN107857426A (en) | A kind of phosphorus-containing wastewater integrated conduct method | |
| CN102328984A (en) | Processing method of waste water in phosphorus chemical industry | |
| CN102115279B (en) | Method for removing phosphorus in sodium hypochlorite wastewater in acetylene cleaning process | |
| CN103787473A (en) | High-stability sewage treating agent and preparation method thereof | |
| CN105174661A (en) | Acid-pickled phosphatized wastewater treatment process | |
| CN102887575B (en) | Technology for recycling recovery of waste sulfuric acid | |
| WO2013174062A1 (en) | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water | |
| CN105217836B (en) | A kind of method using desulfurization wastewater removal phosphor in sewage | |
| CN102583819A (en) | Method for processing waste water generated by extracting copper oxide from acidic corrosion waste fluid | |
| JP4954131B2 (en) | Treatment method of water containing borofluoride | |
| CN104291482A (en) | Treatment method for wastewater containing high-concentration phosphite | |
| CN104163486A (en) | Method for treating glyphosate waste water by using calcium hypochlorite waste water | |
| CN108083400A (en) | A kind of preparation method of phosphorous polyiron sulfate and its application for handling coking wastewater | |
| CN103771629A (en) | Pretreatment technology of hot-galvanizing wastewater | |
| CN106115797A (en) | It is a kind of that catalytic wet persulfate oxidation is desuifurized prepares polymeric ferric sulfate flocculant method | |
| JP6129533B2 (en) | Waste water treatment method and waste water treatment apparatus | |
| CN104787935A (en) | Fluorine-containing wastewater treatment method | |
| CN114349302A (en) | Sludge decrement liquid caustic soda and manufacturing process thereof | |
| CN110255688B (en) | Treatment method of high-concentration ammonia nitrogen wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110810 |