CN1185171C - Treating method for high fluorice acid waste water - Google Patents
Treating method for high fluorice acid waste water Download PDFInfo
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- CN1185171C CN1185171C CNB011380047A CN01138004A CN1185171C CN 1185171 C CN1185171 C CN 1185171C CN B011380047 A CNB011380047 A CN B011380047A CN 01138004 A CN01138004 A CN 01138004A CN 1185171 C CN1185171 C CN 1185171C
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Abstract
The present invention relates to a treating method for acid waste water high containing fluorine and high suspended substances in the production process of phosphatic fertilisers, which is suitable for treating high fluorine acid waste water containing solid suspended substances. The present invention uses calcium carbonate as a main fluorine removing agent and calcium oxide as an auxiliary fluorine removing agent, and partial solid grain stillages are returned to be used as aggregating crystal seed. Control conditions are carried out by that the main fluorine removing agent, the aggregating crystal seed and the auxiliary fluorine removing agent are orderly added, ph value is adjusted from 6 to 9, settlement is carried out to separate solid from treating water, partial grain stillages are returned to the original water, and comprehensive utilization is carried out to partial grain stillages. The present invention has the advantages of wide agent source, low price, short water treatment time, simple technology and low water treatment cost.
Description
Technical field: the invention belongs to environmental technology field, the purifying method of high fluorine-containing, the acidic industrial effluent that contains suspended substance that is specifically related to produce in a kind of phophatic fertilizer production process.
Background technology: the phosphate fertilizer discharged volume of industrial waste water occupies the 3rd in China's chemical industry, and its principal pollutant are fluorochemical, and fluorochemical is mainly derived from the discharging of waste water in the phophatic fertilizer production process.Because produce a large amount of silicon tetrafluorides in the phophatic fertilizer production process, these gas absorption generate silicofluoric acid, silicofluoric acid and sodium-chlor reaction generate Sodium Silicofluoride, produce the waste water of high fluorine, peracid, high suspended matter simultaneously.Wherein fluorine concentration is about 25-8000mg/L; Suspended substance is 600-10000mg/L; PH＜1.The discharging of this class waste water has caused serious harm to water body, farmland and people's living environment.
At present, fluorine-containing wastewater treatment method roughly can reduce three classes by used defluorinating agent: the first kind is carried out chemical precipitation with calcium oxide or magnesium oxide; Second class adopts lime-aluminate coagulating precipitator method; The 3rd class is an absorption method, and it is as the deep treatment method of fluoride waste.
The wastewater treatment fluorine-containing to height, according to pertinent data record when fluorine concentration be that 10000mg/L is when following, with the processing of calcium oxide chemical precipitation method.Practical situation show: it is that very difficult (national grade one discharge standard is a fluorine concentration≤10mg/L), need just can meet the demands through secondary neutralization and two-stage precipitation that neutralization precipitation of high-concentration fluorine-contained waste water is reached discharging standards.In recent years, foreign patent has been introduced the novel method of many processing fluoride wastes, it is to select for use two or three collocation to use in calcium salt, phosphoric acid salt, molysite, aluminium salt that one class is arranged, and defluorination effect is better, for example the treatment process of the flue fluoride waste introduced of Japanese Patent JP62388.But dosing is big; Original concentration to waste water requires low; Handle waste water cost height.For the fluoride waste of high density do not have that technical process is simple at present as yet, less investment, proper method that working cost is low.
Summary of the invention: purpose of the present invention, be to select for use the defluorinating agent cheap, that raw material is easy to get to handle high fluoride waste, reduce the processing costs of waste water effectively; Be to control sedimentary generation and crystalline growth rate, overcome the deficiency that adds flocculation agent in the settling process; Be to solve high fluoride waste breakthroughly and need a secondary or a multiple-stage treatment difficult problem up to standard.
The present invention is achieved like this: adopt one-level neutralizing treatment waste water, promptly in waste water, be sequentially added into main defluorinating agent calcium salt, gathering crystal seed, the auxilliary defluorinating agent alkali of 0-100g/L, adjust pH value 6-9, settlement separately go out solid sediment and treating water, the treating water qualified discharge, a sediment part is returned as assembling crystal seed, another part comprehensive utilization, settling time 0-30 minute.Calcium salt can be a lime carbonate, and auxilliary defluorinating agent is adjusted the pH value with calcium oxide, and assembling crystal seed is sediment Calcium Fluoride (Fluorspan).
The present invention has following evident characteristic:
1 defluorinating agent is selected the technical calcium carbonate cheap, that raw material is easy to get for use, on the one hand in and the acid in the waste water, fluorine bonded calcium ion is provided, produce gas in the reaction process in addition, solid-liquid surface viscous flow film is brought in constant renewal in, improve mass transfer and chemical reaction rate.
Do not need to add any flocculation agent in the 2 sediment settling processes, and settling velocity is fast.
3 high fluoride wastes are handled through one-level just can reach national grade one discharge standard.
4 cost of water treatment are low.
5 waste residues can mix the raw material of producing general calcium or directly mix in the finished product of general calcium, have avoided secondary pollution.
Embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment:
In waste water, add technical grade lime carbonate, sediment Calcium Fluoride (Fluorspan), the add-on of defluorinating agent lime carbonate is 30-60g/L, sediment Calcium Fluoride (Fluorspan) is 0.1-1g/L, stir, reaction 10-25min adds the technical grade calcium oxide and adjusts waste water ph in the 7-8 scope, stir 5-10min, sedimentation, as accumulative crystallization, another part mixes the raw material of producing general calcium or directly mixes in the general calcium finished product solid sediment through the part of dewatering.Clear liquid reaches national grade one discharge standard (fluorine concentration≤10mg/L wherein; Suspended substance≤70mg/L; The pH value is 6-9) directly discharging.
Above-mentioned enforcement adopts one-level to handle the waste water that the production of phosphate fertilizer device is discharged, and its raw water quality sees Table 1; Result sees Table 2.
Table 1 raw water quality
| Sequence number | Substances content (mg/L) | |||
| PH | Suspended substance (acid non-soluble substance) | Total fluorine | Hydrogenchloride (HCl) | |
| 1 | 0.60 | 6100 | 5832 | 2493 |
| 2 | 0.65 | 6200 | 6000 | 2904 |
| 3 | 0..62 | 6400 | 6230 | 2555 |
Table 2 result
| Sequence number | Treatment condition (g/L) | Treating water water quality | ||||||
| Lime carbonate | Calcium oxide | Sediment Calcium Fluoride (Fluorspan) | Supernatant liquor pH value | Filtrate fluorine content (mg/L) | Clear liquor fluorine content (mg/L) | Suspended substance (mg/L) | 3 minutes sinkabilitys (ml) | |
| 1 | 55.6 | 0.75 | 0.2 | 7.67 | 6.34 | 6.84 | 38.8 | 430 |
| 2 | 55.7 | 0.83 | 0.2 | 7.34 | 6.55 | 7.38 | 41.6 | 440 |
| 3 | 55.7 | 0.80 | 0.2 | 7.64 | 6.74 | 6.85 | 40.1 | 430 |
Annotate: 1 test lime carbonate (purity 94.48%), calcium oxide (purity 60%) are respectively technical grade.
2 half an hour sinkability be defined as and measure the 500ml treatment solution, supernatant liquor volume after sedimentation half an hour.
Claims (1)
1, a kind for the treatment of method for high fluorice acid waste water, it is characterized in that adopting one-level neutralizing treatment waste water, promptly add the main defluorinating agent lime carbonate of 30-60g/L in waste water, 0.1-1g/L assembles crystal seed sediment Calcium Fluoride (Fluorspan), stir, reaction 10-25min adds auxilliary defluorinating agent calcium oxide and adjusts pH value 6-9, stirs 5-10min, sedimentation, the solid sediment returns as assembling crystal seed, another part comprehensive utilization, clear liquid direct discharging up to standard through the part of dewatering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB011380047A CN1185171C (en) | 2001-12-20 | 2001-12-20 | Treating method for high fluorice acid waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011380047A CN1185171C (en) | 2001-12-20 | 2001-12-20 | Treating method for high fluorice acid waste water |
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| CN1351968A CN1351968A (en) | 2002-06-05 |
| CN1185171C true CN1185171C (en) | 2005-01-19 |
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| CNB011380047A Expired - Fee Related CN1185171C (en) | 2001-12-20 | 2001-12-20 | Treating method for high fluorice acid waste water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917987A (en) * | 2010-07-28 | 2013-02-06 | 栗田工业株式会社 | Method for treating fluorine-containing water |
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| CN100337930C (en) * | 2005-06-20 | 2007-09-19 | 许庆华 | Attapulgite defluorination agent |
| CN101288845B (en) * | 2008-05-19 | 2010-06-02 | 杨劭 | Preparation method of compound absorbent filter medium for removing florin, iron and manganese of water treatment |
| CN102276034B (en) * | 2011-07-19 | 2013-05-08 | 上海电力学院 | Process method for removing fluorides in high concentrations of fluoride-containing wastewater from thermal power plant |
| CN102502553A (en) * | 2011-09-30 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for preparing feed grade calcium hydrogen phosphate from waste water of phosphate fertilizer plant |
| CN103011453B (en) * | 2012-12-08 | 2014-01-22 | 北京国环清华环境工程设计研究院有限公司 | Processing method for fluoride waste water in production of solar cells |
| CN104591462B (en) * | 2015-01-15 | 2016-08-24 | 桂林电子科技大学 | A kind of fluoride coprecipitation processing highly acid height fluorine waste water |
| CN106698730A (en) * | 2015-07-28 | 2017-05-24 | 江苏吉华化工有限公司 | Phosphorus chemical wastewater treatment method |
| CN106167272A (en) * | 2016-02-23 | 2016-11-30 | 瓮福（集团）有限责任公司 | Utilize the method that Phosphate Fertilizer Industry waste water produces feed grade calcium carbonate |
| CN105836952A (en) * | 2016-05-25 | 2016-08-10 | 海南宝来工贸有限公司 | Solar silicon washing waste acid treatment device and method |
| EP3495327A1 (en) * | 2017-12-06 | 2019-06-12 | Ovivo Inc. | Treatment of fluoride-containing wastewater |
| CN109851020A (en) * | 2019-02-13 | 2019-06-07 | 江西沃格光电股份有限公司 | Waste water treating agent and preparation method thereof and wastewater treatment method |
| CN109987747A (en) * | 2019-04-19 | 2019-07-09 | 南京乐透思环保科技有限公司 | A kind of photovoltaic wastewater inorganic agent and its processing equipment and processing method |
| CN110078109A (en) * | 2019-05-21 | 2019-08-02 | 江苏省环境科学研究院 | A method of high-purity is fluorinated calcium product from acidic fluorine-containing waste water |
| CN110255692A (en) * | 2019-07-05 | 2019-09-20 | 江苏南大环保科技有限公司 | In a kind of photovoltaic industry concentrated acid wastewater by sequencing batch formula and accurate control method |
| CN111439865B (en) * | 2020-04-07 | 2022-02-25 | 中国科学院生态环境研究中心 | Defluorination method for coal gas wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917987A (en) * | 2010-07-28 | 2013-02-06 | 栗田工业株式会社 | Method for treating fluorine-containing water |
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