CN1351968A - Treating method for high fluorice acid waste water - Google Patents

Treating method for high fluorice acid waste water Download PDF

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Publication number
CN1351968A
CN1351968A CN 01138004 CN01138004A CN1351968A CN 1351968 A CN1351968 A CN 1351968A CN 01138004 CN01138004 CN 01138004 CN 01138004 A CN01138004 A CN 01138004A CN 1351968 A CN1351968 A CN 1351968A
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China
Prior art keywords
waste water
defluorinating agent
fluorice
treatment
acid waste
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CN 01138004
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Chinese (zh)
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CN1185171C (en
Inventor
李国平
魏兰
丁健华
韩文平
邵永春
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南化集团研究院
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Priority to CNB011380047A priority Critical patent/CN1185171C/en
Publication of CN1351968A publication Critical patent/CN1351968A/en
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Publication of CN1185171C publication Critical patent/CN1185171C/en

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Abstract

A treating process for high-fluoric acid waste water containing high-suspended solid matter adopts calcium carbonate as main defluorinating agent and calcium oxide as auxiliary defluorinating agent, and returns partial settled solid dregs as aggregating crystal sead. It includes successive steps of adding main defluorinating agent, auxiliary defluorinating agent and aggregating crystal seed, pH regulation to 6-9, settling and separating solid matter, returning partial settled dregs to source water, and comprehensively utilizing other settled dregs. The present invention has low water treating cost, short water treating period and simple technological process.

Description

Treating method for high fluorice acid waste water
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 250-8000mg/L; Suspended substance is 6000-10000mg/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 (4)

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 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.
2, a kind for the treatment of method for high fluorice acid waste water as claimed in claim 1 is characterized in that described calcium salt is a lime carbonate.
3, a kind for the treatment of method for high fluorice acid waste water as claimed in claim 1 is characterized in that assisting defluorinating agent and adjusts the pH value with calcium oxide.
4, a kind for the treatment of method for high fluorice acid waste water as claimed in claim 1 is characterized in that sediment Calcium Fluoride (Fluorspan) is as assembling crystal seed.
CNB011380047A 2001-12-20 2001-12-20 Treating method for high fluorice acid waste water CN1185171C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102276034A (en) * 2011-07-19 2011-12-14 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
CN103011453A (en) * 2012-12-08 2013-04-03 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
CN104591462A (en) * 2015-01-15 2015-05-06 桂林电子科技大学 Fluoride coprecipitation method for treating strong-acidity high-fluorine wastewater
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
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
CN106698730A (en) * 2015-07-28 2017-05-24 江苏吉华化工有限公司 Phosphorus chemical 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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5644236B2 (en) * 2010-07-28 2014-12-24 栗田工業株式会社 Fluorine-containing water treatment method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102276034A (en) * 2011-07-19 2011-12-14 上海电力学院 Process method for removing fluorides in high concentrations of fluoride-containing wastewater from thermal power plant
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
CN103011453A (en) * 2012-12-08 2013-04-03 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
CN104591462A (en) * 2015-01-15 2015-05-06 桂林电子科技大学 Fluoride coprecipitation method for treating strong-acidity high-fluorine wastewater
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
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

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